Fluorinated ether compound, fluorinated ether composition, coating liquid and article

ABSTRACT

To provide a fluorinated ether compound, a fluorinated ether composition and a coating liquid that are able to form a surface layer which is excellent in water/oil repellency, abrasion resistance, fingerprint stain removability, lubricity and outer appearance, and an article having such a surface layer. A fluorinated ether compound represented by A 1 -O—(R f1 O) m1 -Q 1 -[C(O)N(R 1 )] p1 —R 11 —C[—R 12 —SiR 13   n1 X 1   3-n1 ] 3 , wherein A 1  is a C 1-20  perfluoroalkyl group; R f1  is a fluoroalkylene group having no branched structure; m1 is an integer from 2 to 210; Q 1  is a single bond or a fluoroalkylene group having no branched structure; R 1  is a hydrogen atom, etc.; p1 is 0 or 1; R 11  is a single bond, an alkylene group, etc.; R 12  is an alkylene group, etc.; R 13  is a monovalent hydrocarbon group, etc.; X 1  is a hydrolyzable group; and n1 is an integer of from 0 to 2.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patentapplication Ser. No. 15/877,489, filed Jan. 23, 2018, now U.S. Pat. No.10,550,288, which is in turn a continuation of PCT Application No.PCT/JP2016/075354, filed on Aug. 30, 2016, which is based upon andclaims the benefit of priority from Japanese Patent Application No.2015-171986 filed on Sep. 1, 2015. The contents of those applicationsare incorporated herein by reference in their entireties.

TECHNICAL FIELD

The present invention relates to a fluorinated ether compound, afluorinated ether composition, a coating liquid and an article.

BACKGROUND ART

A fluorinated compound exhibits high lubricity, water/oil repellency,etc. and thus is suitably used for a surface treatment agent. Whenwater/oil repellency is imparted to the surface of a substrate by such asurface treatment agent, it will be easy to wipe off stain from thesurface of the substrate, whereby removability of stain will beimproved. Among such fluorinated compounds, a fluorinated ether compoundhaving a poly(oxyperfluoroalkylene) chain with an ether bond (—O—)present at middle in a perfluoroalkyl chain, is particularly excellentin removability of stain of e.g. oils or fats.

A surface treatment agent containing the fluorinated ether compound isused in an application where it is desired to maintain, for a longperiod of time, a performance (abrasion resistance) whereby water/oilrepellency is less likely to be lowered even if rubbed repeatedly with afinger, and a performance (fingerprint stain removability) whereby afingerprint adhered to a surface can be readily removed by wiping, forexample, as a surface treatment agent for a member constituting thesurface to be touched with a finger, of a touch panel.

In order to impart abrasion resistance to the surface layer formed onthe surface of a substrate, for example, a hydrolyzable silyl group maybe introduced at a terminal of the fluorinated ether compound, so thatthe fluorinated ether compound and the substrate will be chemicallybonded. As a fluorinated ether compound for the purpose of forming asurface layer excellent in abrasion resistance, a fluorinated ethercompound has been proposed wherein to each of both terminals of thefluorinated ether compound, three hydrolyzable silyl groups areintroduced via a branched structure by pentaerythritol (Patent Document1).

PRIOR ART DOCUMENT Patent Document

Patent Document 1: JP-A-2014-070163

DISCLOSURE OF INVENTION Technical Problem

According to the findings by the present inventors, the fluorinatedether compound described in Patent Document 1 has the followingproblems.

-   -   Both terminals of the fluorinated ether compound are        immobilized, as hydrolyzable silyl groups at both terminals are        reacted with the substrate, or by an intermolecular reaction.        Therefore, lubricity (smoothness when the surface layer is        touched with a finger) and abrasion resistance of the surface        layer become insufficient.    -   The poly(oxyperfluoroalkylene) chain has a branched structure,        whereby fingerprint stain removal properties and lubricity of        the surface layer become insufficient.    -   Since the content of non-fluorinated portions (a branched        structure by pentaerythritol and three hydrolyzable silyl        groups) at terminals, is large, the outer appearance of the        surface layer tends to be deteriorated. The reason is considered        to be such that among molecules of the fluorinated ether        compound, hydrolyzable silyl groups are likely to be        agglomerated one another, and in the coating liquid, or during        drying after the coating liquid is applied to the surface of a        substrate, hydrolyzable silyl groups will be agglomerated and        reacted one another to form a non-uniform layer.

An object of the present invention is to provide a fluorinated ethercompound, a fluorinated ether composition and a coating liquid, capableof forming a surface layer excellent in water/oil repellency, abrasionresistance, fingerprint stain removability, lubricity and outerappearance, and an article having a surface layer excellent in water/oilrepellency, abrasion resistance, fingerprint stain removability,lubricity and outer appearance.

Solution to Problem

The present invention provides a fluorinated ether compound, afluorinated ether composition, a coating liquid and an article havingthe following constructions [1] to [14].

-   [1] A fluorinated ether compound represented by the following    formula (1):    A¹-O—(R^(f1)O)_(m1)-Q¹-[C(O)N(R¹)]_(p1)—R¹¹—C[—R¹²—SiR¹³ _(n1)X¹    _(3-n1)]₃  (1)    wherein

A¹ is a C₁₋₂₀ perfluoroalkyl group,

R^(f1) is a fluoroalkylene group having no branched structure,

m1 is an integer of from 2 to 210,

(R^(f1)O)_(m1) may be one composed of at least two types of R^(f1)O,

Q¹ is a single bond or a fluoroalkylene group having no branchedstructure,

R¹ is a hydrogen atom or an alkyl group,

p1 is 0 or 1,

R¹¹ is a single bond, an alkylene group, an alkylene group having anetheric oxygen atom at its terminal (which is the terminal on the sidebonded to C[—R¹²—SiR¹³ _(n1)X¹ _(3-n1)]₃), an alkylene group with atleast two carbon atoms, having an etheric oxygen atom between itscarbon-carbon atoms, or an alkylene group with at least two carbonatoms, having an etheric oxygen atom between its carbon-carbon atoms andat its terminal (which is the terminal on the side bonded toC[—R¹²—SiR¹³ _(n1)X¹ _(3-n1)]₃),

R¹² is an alkylene group, an alkylene group having an etheric oxygenatom at its terminal (but excluding the terminal on the side bonded toSi), or an alkylene group with at least two carbon atoms, having anetheric oxygen atom between its carbon-carbon atoms,

R¹³ is a hydrogen atom or a monovalent hydrocarbon group,

X¹ is a hydrolyzable group,

n1 is an integer of from 0 to 2, and

three [—R¹²—SiR¹³ _(n1)X¹ _(3-n1)] may not be all the same group.

-   [2] The fluorinated ether compound according to [1], wherein the    fluorinated ether compound represented by the formula (1) is a    fluorinated ether compound represented by the following formula    (1-1):    A¹-O—(R^(f5)O)_(m5)(R^(F1)O)_(m10)(R^(f6)O)_(m6)-Q¹-[C(O)N(R¹)]_(p1)—R¹¹—C[—R¹²—SiR¹³    _(n1)X¹ _(3-n1)]₃  (1-1)    wherein A¹, Q¹, R¹, p1, R¹¹, R¹², R¹³, X¹ and n1 are the same as in    the formula (1),

R^(F1) is a perfluoroalkylene group having no branched structure, m10 isan integer of at least 2, and (R^(F1)O)_(m10) may be one composed of atleast two types of R^(F1)O,

R^(f5) is a fluoroalkylene group containing at least one hydrogen atomand having no branched structure, m5 is an integer of from 0 to 4, andwhen m5 is an integer of from 2 to 4, (R^(f5)O)_(m5) may be one composedof at least two types of R^(f5)O,

R^(f6) is a fluoroalkylene group containing at least one hydrogen atomand having no branched structure, m6 is an integer of from 0 to 4, andwhen m6 is an integer of from 2 to 4, (R^(f6)O)_(m6) may be one composedof at least two types of R^(f6)O, andm10+m5+m6=m1.

-   [3] The fluorinated ether compound according to [2], wherein R^(F1)    is a C₁₋₆ perfluoroalkylene group, and R^(f5) and R^(f6) are each    independently a C₂₋₆ fluoroalkylene group.-   [4] The fluorinated ether compound according to [2] or [3], wherein    R^(f5) and R^(f6) are each independently a fluoroalkylene group    having one or two hydrogen atoms.-   [5] The fluorinated ether compound according to any one of [2] to    [4], wherein

when p1 is 0, m6 is 1 or 2 and Q¹ is a single bond, and (R^(f6)O) bondedto R¹¹ is a group represented by (R^(f7)CH₂O), and

when p1 is 1, m6 is 0 and Q¹ is a fluoroalkylene group.

-   [6] The fluorinated ether compound according to any one of [2] to    [5], wherein m10 is at least 5.-   [7] The fluorinated ether compound according to any one of [1] to    [6], wherein when Q¹ is a fluoroalkylene group, such a    fluoroalkylene group is a C₁₋₆ perfluoroalkylene group.-   [8] The fluorinated ether compound according to any one of [1] to    [7], wherein

when p1 is 0, R¹¹ is a C₁₋₄ alkylene group, and

when p1 is 1, R¹¹ is a single bond or a C₁₋₄ alkylene group.

-   [9] The fluorinated ether compound according to any one of [1] to    [8], wherein R¹² is a C₂₋₆ alkylene group, or a C₃₋₈ alkylene group    having an etheric oxygen atom between carbon atoms.-   [10] The fluorinated ether compound according to any one of [1] to    [9], which has a number average molecular weight of from 500 to    20,000.-   [11] A fluorinated ether composition comprising the fluorinated    ether compound as defined any one of [1] to [10], and a fluorinated    ether compound other than the fluorinated ether compound represented    by the formula (1), characterized in that

the total proportion of the fluorinated ether compound represented bythe formula (1) and other fluorinated ether compound in the fluorinatedether composition is from 80 to 100 mass %, and

the proportion of said other fluorinated ether compound to the total ofthe fluorinated ether compound represented by the formula (1) and otherfluorinated ether compound is more than 0 mass % and less than 40 mass%.

-   [12] The fluorinated ether composition according to [11], wherein    said other fluorinated ether compound is at least one member    selected from the group consisting of the following fluorinated    ether compound (2), the following fluorinated ether compound (3) and    the following fluorinated ether compound (4):

Fluorinated ether compound (2): A fluorinated ether compound wherein inthe fluorinated ether compound represented by the formula (1), a grouphaving said —C[—R¹²—SiR¹³ _(n1)X¹ _(3-n1)]₃ is bonded to both sides ofsaid (R^(f1)O)_(m1),

Fluorinated ether compound (3): A fluorinated ether compound wherein inthe fluorinated ether compound represented by the formula (1), a grouphaving said A¹ is bonded to both sides of said (R^(f1)O)_(m1),

Fluorinated ether compound (4): A fluorinated ether compound wherein inthe fluorinated ether compound represented by the formula (1), said—C[—R¹²—SiR¹³ _(n1)X¹ _(3-n1)]₃ is substituted by —C[—R¹²—SiR¹³ _(n1)X¹_(3-n1)]_(3-t)[—R¹⁵]_(t) (wherein R¹⁵ is an unsaturated bond-containinggroup which becomes —R¹²—SiR¹³ _(n1)X¹ _(3-n1) by addition of HSiR¹³_(n1)X¹ _(3-n1), or an isomer group of the unsaturated bond-containinggroup, and t is an integer of 1 to 3).

-   [13] A coating liquid characterized by comprising a fluorinated    ether compound as defined in any one of [1] to [10] or a fluorinated    ether composition as defined in [11] or [12], and a liquid medium.-   [14] An article characterized by having a surface layer which is    formed of a fluorinated ether compound as defined in any one of [1]    to [10] or a fluorinated ether composition as defined in [11] or    [12].

Advantageous Effects of Invention

According to the fluorinated ether compound, the fluorinated ethercomposition and the coating liquid of the present invention, it ispossible to form a surface layer excellent in water/oil repellency,abrasion resistance, fingerprint stain removability, lubricity and outerappearance.

The article of the present invention has a surface layer excellent inwater/oil repellency, abrasion resistance, fingerprint stainremovability, lubricity and outer appearance.

DESCRIPTION OF EMBODIMENTS

In this specification, a compound represented by the formula (1) will bereferred to as a compound (1). Compounds represented by other formulaewill be referred to in the same manner.

Meanings of the following terms in this specification are as follows.

A “perfluoroalkyl group” means a group having all of hydrogen atoms inan alkyl group substituted by fluorine atoms.

A “fluoroalkylene group” means a group having at least one of hydrogenatoms in an alkylene group substituted by a fluorine atom.

A “perfluoroalkylene group” means a group having all of hydrogen atomsin an alkylene group substituted by fluorine atoms.

The chemical formula of an oxyperfluoroalkylene group shall be writtenby placing its oxygen atom on the right hand side of theperfluoroalkylene group.

An “etheric oxygen atom” means an oxygen atom to form an ether bond(—O—) between carbon-carbon atoms.

A “hydrolyzable silyl group” means a group capable of forming a silanolgroup (Si—OH) by hydrolysis. For example, it is SiR¹³ _(n1)X¹ _(3-n1) inthe formula (1).

A “surface layer” means a layer formed at the surface of a substrate.

The “number average molecular weight” of a fluorinated ether compound iscalculated by the following method by using a NMR analysis.

It is calculated by obtaining the number (average value) ofoxyperfluoroalkylene groups based on terminal groups, by ¹H-NMR and¹⁹F-NMR. The terminal groups may, for example, be A¹ or SiR¹³ _(n1)X¹_(3-n1) in the formula (1).

[Fluorinated Ether Compound]

The fluorinated ether compound of the present invention (hereinafterreferred to also as the present compound) is the compound (1).A¹-O—(R^(f1)O)_(m1)-Q¹-[C(O)N(R¹)]_(p1)—R¹¹—C[—R¹²—SiR¹³ _(n1)X¹_(3-n1)]₃  (1)wherein A¹ is a C₁₋₂₀ perfluoroalkyl group; R^(f1) is a fluoroalkylenegroup having no branched structure; m1 is an integer of from 2 to 210;(R^(f1)O)_(m1) may be one composed of at least two types of R^(f1)O; Q¹is a single bond or a fluoroalkylene group having no branched structure;R¹ is a hydrogen atom or an alkyl group; p1 is 0 or 1; R¹¹ is a singlebond, an alkylene group, an alkylene group having an etheric oxygen atomat its terminal (which is the terminal on the side bonded toC[—R¹²—SiR¹³ _(n1)X¹ _(3-n1)]₃), an alkylene group with at least twocarbon atoms, having an etheric oxygen atom between its carbon-carbonatoms, or an alkylene group with at least two carbon atoms, having anetheric oxygen atom between its carbon-carbon atoms and at its terminal(which is the terminal on the side bonded to C[—R¹²—SiR¹³ _(n1)X¹_(3-n1)]₃); R¹² is an alkylene group, an alkylene group having anetheric oxygen atom at its terminal (but excluding the terminal on theside bonded to Si), or an alkylene group with at least two carbon atoms,having an etheric oxygen atom between its carbon-carbon atoms; R¹³ is ahydrogen atom or a monovalent hydrocarbon group; X¹ is a hydrolyzablegroup; n1 is an integer of from 0 to 2; and three [—R¹²—SiR¹³ _(n1)X¹_(3-n1)] may not be all the same group.(A¹ Group)

As A¹, from the viewpoint of further excellency in lubricity andabrasion resistance of the surface layer, a C₁₋₁₀ perfluoroalkyl groupis preferred, a C₁₋₆ perfluoroalkyl group is more preferred, and a C₁₋₃perfluoroalkyl group is particularly preferred.

A¹ has CF₃— at its terminal, whereby one terminal of the compound (1)becomes CF₃— and the other terminal becomes a hydrolyzable silyl group.According to the compound (1) having such a structure, a surface layerwith a low surface energy can be formed, and such a surface layer isexcellent in lubricity and abrasion resistance. On the other hand,according to the conventional fluorinated ether compound havinghydrolyzable silyl groups at both terminals, lubricity and abrasionresistance of the surface layer are insufficient.

((R^(f1)O)_(m1))

R^(f1) may be a perfluoroalkylene group having no branched structure, ora fluoroalkylene group containing at least one hydrogen atom and havingno branched structure.

As R^(f1), from the viewpoint of further excellency in abrasionresistance and fingerprint stain removability of the surface layer, aC₁₋₆ fluoroalkylene group having no branched structure is preferred, aC₁₋₄ fluoroalkylene group having no branched structure is morepreferred, and from the viewpoint of further excellency in lubricity ofthe surface layer, particularly preferred is a C₁₋₂ fluoroalkylene grouphaving no branched structure.

The compound (1) has (R^(f1)O)_(m1), and thus, the content of fluorineatoms is large. Therefore, it is possible to form a surface layerexcellent in water/oil repellency, abrasion resistance and fingerprintstain removability.

Further, since R^(f1) is a fluoroalkylene group having no branchedstructure, (R^(f1)O)_(m1) becomes a linear structure. According to thecompound (1) of such a structure, the surface layer will be excellent inabrasion resistance and lubricity. On the other hand, according to theconventional fluorinated ether compound wherein apoly(oxyperfluoroalkylene) chain has a branched structure, abrasionresistance and lubricity of the surface layer are insufficient.

m1 is an integer of from 2 to 210, preferably an integer of from 5 to160, particularly preferably an integer of from 10 to 110. When m1 is atleast the lower limit value in the above range, water/oil repellency ofthe surface layer will be excellent. When m1 is at most the upper limitvalue in the above range, abrasion resistance of the surface layer willbe excellent. That is, if the number average molecular weight of thecompound (1) is too large, the number of hydrolyzable silyl groupspresent per unit molecular weight decreases, whereby abrasion resistancedecreases.

In (R^(f1)O)_(m1), in a case where at least two types of R^(f1)O arepresent, the bonding order of such plural types of R^(f1)O is notlimited. For example, in a case where two types of R^(f1)O are present,such two types of R^(f1)O may be arranged randomly, alternately or inblocks.

At least two types of R^(f1)O being present is meant that in a casewhere R^(f1) is a perfluoroalkylene group, at least two types of R^(f1)Odifferent in the number of carbon atoms are present. In a case whereR^(f1) is a fluoroalkylene group having hydrogen atoms, it is meant thatat least two types of R^(f1)O different in at least one of the number ofcarbon atoms, the number of hydrogen atoms and the bonding positions ofhydrogen atoms, are present.

With respect to the arrangement of at least two types of R^(f1)O, forexample in the case of fluorinated ether compounds in Examples, thestructure represented by {(CF₂O)_(x1)(CF₂CF₂O)_(x2)} indicates that x1pieces of (CF₂O) and x2 pieces of (CF₂CF₂O) are randomly arranged.Further, the structure represented by (CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3)indicates that x3 pieces of (CF₂CF₂O) and x3 pieces of (CF₂CF₂CF₂CF₂O)are arranged alternately.

(Q¹ Group)

Q¹ may be a single bond, a perfluoroalkylene group having no branchedstructure, or a fluoroalkylene group containing at least one hydrogenatom and having no branched structure. According to the compound (1)wherein Q¹ has no branched structure, it is possible to form a surfacelayer excellent in abrasion resistance and lubricity.

Q¹ may be a fluoroalkylene group derived from R^(f1), or afluoroalkylene group derived from a compound (e.g. later-describedcompound (30)) having an amide group and a hydrolyzable silyl group usedin preparing the compound (1).

When Q¹ is not a single bond, the number of carbon atoms is preferablyfrom 1 to 10.

([C(O)N(R¹)]_(p1) Group)

When p1 is 0 or 1, there is no substantial difference in characteristicsof the fluorinated ether compound. When p1 is 1, the compound has anamide bond, but since at least one fluorine atom is bonded to theterminal carbon atom of Q¹ on the side bonded to [C(O)N(R¹)], thepolarity of the amide bond tends to be small, and the water/oilrepellency of the surface layer is less likely to be low. Whether p1should be 0 or 1, may be selected from the viewpoint of the productionefficiency.

R¹ in the [C(O)N(R¹)]_(p1) group is, from the viewpoint of productionefficiency of the compound (1), preferably a hydrogen atom.

When R¹ is an alkyl group, such an alkyl group is preferably a C₁₋₄alkyl group.

(R¹¹ Group)

As R¹¹, a single bond, a C₁₋₁₀ alkylene group, a C₁₋₁₀ alkylene grouphaving an etheric oxygen atom at its terminal (which is the terminal onthe side bonded to C[—R¹²—SiR¹³ _(n1)X¹ _(3-n1)]₃), a C₂₋₁₀ alkylenegroup having an etheric oxygen atom between its carbon-carbon atoms, ora C₂₋₁₀ alkylene group having an etheric oxygen atom between itscarbon-carbon atoms and at its terminal (which is the terminal on theside bonded to C[—R¹²—SiR¹³ _(n1)X¹ _(3-n1)]₃), is preferred.

When p1 is 0, R¹¹ is, from the viewpoint of production efficiency of thecompound (1), preferably a single bond or an alkylene group having atmost 4 carbon atoms, more preferably a single bond, a methylene group ora dimethylene group. The group having an etheric oxygen atom may, forexample, be —CH₂CH₂O—, —CH₂CH₂OCH₂—, etc.

When p1 is 1, R¹¹ is, from the viewpoint of production efficiency of thecompound (1), preferably a single bond or an alkylene group having atmost 4 carbon atoms, more preferably a single bond, a methylene group ora dimethylene group.

(R¹² Group)

As R¹², a C₁₋₁₀ alkylene group, a C₁₋₁₀ alkylene group having an ethericoxygen atom at its terminal (but excluding the terminal on the sidebonded to Si), or a C₂₋₁₀ alkylene group having an etheric oxygen atombetween its carbon-carbon atoms. From the viewpoint of productionefficiency of the compound (1), a group selected from the groupconsisting of —CH₂CH₂—, —CH₂CH₂CH₂—, —CH₂OCH₂CH₂CH₂—,—CH₂OCH₂CH₂CH₂CH₂CH₂— and —OCH₂CH₂CH₂— (provided that the right handside is bonded to Si), is preferred.

As R¹², from the viewpoint of excellent light resistance of the surfacelayer, one having no etheric oxygen atom is particularly preferred. In atouch panel for outdoor use (digital signage of vending machines, guideplates, etc.), a touch panel mounted on a vehicle or the like, thesurface layer is required to have light resistance.

Three R¹² in the compound (1) may be all the same group, or may not beall the same group.

(SiR¹³ _(n1)X¹ _(3-n1) Group)

SiR¹³ _(n1)X¹ _(3-n1) is a hydrolyzable silyl group.

The compound (1) has three hydrolyzable silyl groups at its terminal.The compound (1) of such a structure is chemically firmly bonded to asubstrate, whereby the surface layer is excellent in abrasionresistance.

Further, the compound (1) has hydrolyzable silyl groups only at oneterminal. The compound (1) of such a structure tends to be hardlyagglomerated, so that the surface layer will be excellent in outerappearance.

X¹ is a hydrolyzable group. The hydrolyzable group is a group whichbecomes a hydroxy group by a hydrolysis reaction. That is, Si—X¹ at theterminal of the compound (1) becomes a silanol group (Si—OH) by ahydrolysis reaction. Silanol groups are further intermolecularly reactedto form Si—O—Si bonds. Further, a silanol group will be reacted fordehydration condensation with a hydroxy group (substrate-OH) at thesurface of the substrate, to form a chemical bond (substrate-O—Si).

X¹ may, for example, be an alkoxy group, a halogen atom, an acyl group,an isocyanate group (—NCO), etc. The alkoxy group is preferably a C₁₋₄alkoxy group.

As X¹, from the viewpoint of production efficiency of the compound (1),a C₁₋₄ alkoxy group or a halogen atom is preferred. As the halogen atom,a chlorine atom is particularly preferred. As X¹, from such a viewpointthat outgassing is less during coating, and storage stability of thecompound (1) is excellent, a C₁₋₄ alkoxy group is preferred; in a casewhere long-term storage stability of the compound (1) is required, anethoxy group is particularly preferred; and in order to shorten thereaction time after coating, a methoxy group is particularly preferred.

R¹³ is a hydrogen atom or a monovalent hydrocarbon group. The monovalenthydrocarbon group may, for example, be an alkyl group, a cycloalkylgroup, an alkenyl group, an allyl group, etc.

As R¹³, a monovalent hydrocarbon group is preferred, and a monovalentsaturated hydrocarbon group is particularly preferred. The number ofcarbon atoms in the monovalent saturated hydrocarbon group is preferablyfrom 1 to 6, more preferably from 1 to 3, particularly preferably 1 or2. When the number of carbon atoms in R¹³ is within such a range, it iseasy to produce the compound (1).

n1 is preferably 0 or 1, and 0 is particularly preferred. By thepresence of a plurality of X¹ in one hydrolyzable silyl group, adhesionto the substrate becomes stronger.

As SiR¹³ _(n1)X¹ _(3-n1), Si(OCH₃)₃, SiCH₃(OCH₃)₂, Si(OCH₂CH₃)₃, SiCl₃,Si(OCOCH₃)₃, or Si(NCO)₃ is preferred. From the viewpoint of handlingefficiency in industrial production, Si(OCH₃)₃ is particularlypreferred.

Three SiR¹³ _(n1)X¹ _(3-n1) in the compound (1) may be all the samegroup, or may not be all the same group. From the viewpoint ofproduction efficiency of the compound (1), it is preferred that all arethe same group.

(Preferred Form of Compound (1))

As the compound (1), from such a viewpoint that abrasion resistance andfingerprint stain removability of the surface layer will be furtherimproved, a compound (1-1) is preferred.A¹-O—(R^(f5)O)_(m5)(R^(F1)O)_(m10)(R^(f6)O)_(m6)-Q¹-[C(O)N(R¹)]_(p1)—R¹¹—C[—R¹²—SiR¹³_(n1)X¹ _(3-n1)]₃  (1-1)wherein A¹, Q¹, R¹, p1, R¹¹, R¹², R¹³, X¹ and n1 are the same as in theformula (1),

R^(F1) is a perfluoroalkylene group having no branched structure, m10 isan integer of at least 2, and (R^(F1)O)_(m10) may be one composed of atleast two types of R^(F1)O,

R^(f5) is a fluoroalkylene group containing at least one hydrogen atomand having no branched structure, m5 is an integer of from 0 to 4, andwhen m5 is an integer of from 2 to 4, (R^(f5)O)_(m5) may be one composedof at least two types of R^(f5)O,

R^(f6) is a fluoroalkylene group containing at least one hydrogen atomand having no branched structure, m6 is an integer of from 0 to 4, andwhen m6 is an integer of from 2 to 4, (R^(f6)O)_(m6) may be one composedof at least two types of R^(f6)O, andm10+m5+m6=m1.((R^(f5)O)_(m5))

R^(f5) is a fluoroalkylene group containing at least one hydrogen atomand having no branched structure, preferably a C₂₋₆ fluoroalkylenegroup, particularly preferably a C₂ fluoroalkylene group. The number ofhydrogen atoms is preferably from 1 to 4, particularly preferably 1 or2. As (R^(f5)O), (CHFCF₂O) and (CH₂CF₂O) are preferred.

m5 is preferably an integer of from 0 to 2, more preferably 0 or 2. Whenm is 2, (R^(f5)O)₂ is preferably (CHFCF₂O)—(CH₂CF₂O).

((R^(F1)O)_(m10))

As R^(F1), from such a viewpoint that abrasion resistance andfingerprint stain removability of the surface layer will be furtherimproved, a C₁₋₆ perfluoroalkylene group having no branched structure ispreferred, and a C₁₋₄ perfluoroalkylene group having no branchedstructure is more preferred; and from such a viewpoint that lubricity ofthe surface layer will be further improved, a C₁₋₂ perfluoroalkylenegroup having no branched structure is particularly preferred.

Since the compound (1-1) has (R^(F1)O)_(m10), the content of fluorineatoms is higher. Therefore, it is possible to form a surface layerfurther excellent in water/oil repellency, abrasion resistance andfingerprint stain removability.

Further, since R^(F1) is a perfluoroalkylene group having no branchedstructure, (R^(F1)O)_(m10) becomes to have a straight chain structure.According to the compound (1-1) of such a structure, abrasion resistanceand lubricity of the surface layer will be excellent.

In (R^(F1)O)_(m10), when at least two types of R^(F1)O different innumber of carbon atoms are present, the bonding order of such pluraltypes of R^(F1)O is not limited. For example, when CF₂O and CF₂CF₂O arepresent, such CF₂O and CF₂CF₂O may be arranged randomly, alternately orin block.

As (R^(F1)O)_(m10), from such a viewpoint that the surface layer will befurther excellent in abrasion resistance, fingerprint stain removabilityand lubricity, (CF₂O)_(m11)(CF₂CF₂O)_(m12), (CF₂CF₂O)_(m13),(CF₂CF₂CF₂O)_(m14), or (CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(m15) is preferred, and(CF₂O)_(m11)(CF₂CF₂O)_(m12) is particularly preferred.

Here, m11 is an integer of at least 1, m12 is an integer of at least 1,and the bonding order of m11 pieces of CF₂O and m12 pieces of CF₂CF₂O isnot limited. Preferred is a randomly arranged structure represented by{(CF₂O)_(m11)(CF₂CF₂O)_(m12)}. m13 and m14 are each an integer of from 2to 200, and m15 is an integer of from 1 to 100.

((R^(f6)O)_(m6))

R^(f6) is a fluoroalkylene group containing at least one hydrogen atomand having no branched structure, preferably a C₂₋₆ fluoroalkylenegroup. The number of hydrogen atoms is preferably from 1 to 4,particularly preferably 1 or 2. m6 is preferably from 0 to 2.

In a case where p1 is 0, Q¹ is preferably a single bond. In such a case(i.e. a case where (R^(f6)O)_(m6) and R¹¹ are directly bonded), in(R^(f6)O)_(m6), (R^(f6)O) bonding directly to R¹¹ is preferably a grouprepresented by (R^(f7)CH₂O). R^(f7) is a group having the number ofcarbon atoms less by one than R^(f6), and is a perfluoroalkylene groupor a fluoroalkylene group having hydrogen atom(s). R^(f7) is preferablya perfluoroalkylene group. As specific (R^(f7)CH₂O), (CF₂CH₂O),(CF₂CF₂CH₂O), (CF₂CF₂CF₂CH₂O), (CF₂CF₂CF₂CF₂CH₂O), etc. are preferred.In such a case, m6 is preferably 1.

In a case where p1 is 1, it is preferred that m6 is from 0 to 2, and Q¹is a fluoroalkylene group. In such a case, Q¹ is preferably aperfluoroalkylene group. The number of carbon atoms in Q¹ being aperfluoroalkylene group is more preferably from 1 to 6.

m10+m5+m6 is an integer of from 2 to 200, preferably an integer of from5 to 150, particularly preferably an integer of from 10 to 110. Whenm10+m5+m6 is at least the lower limit value in the above range, thesurface layer will be excellent in water/oil repellency. When m10+m5+m6is at most the upper limit value in the above range, the surface layerwill be excellent in abrasion resistance. That is, if the number averagemolecular weight of the compound (1-1) is too large, the number ofhydrolyzable silyl groups present per unit molecular weight decreases,whereby the abrasion resistance decreases.

m10 is more preferably an integer of at least 5, particularly preferablyat least 10.

(Preferred Form of Compound (1-1))

As the compound (1-1), for example, compounds of the following formulaemay be mentioned. Such compounds are preferred from such a viewpointthat it is easy to produce them industrially, it is easy to handle them,and the surface layer will be further excellent in water/oil repellency,abrasion resistance, fingerprint stain removability, lubricity and outerappearance.

Compound (1-1) wherein Q¹ is a single bond and p1=0.

Here, in the following formulae, “PFPE-CH₂O—” and other “PFPE-”represent A¹-O—(R^(f5)O)_(m5)(R^(F1)O)_(m10)(R^(f6)O)_(m6)—.

Compound (1-1) wherein Q¹ is a perfluoroalkylene group and p1=1.

Here, in the chemical formulae, “PFPE-R^(F)—” representsA¹-O—(R^(f5)O)_(m5)(R^(F1)O)_(m10)(R^(f6)O)_(m6)-Q¹-.

(Method for Producing Compound (1))

In a case where p1 is 0, as the method for producing the compound (1),for example, the following methods (10) to (15) may be mentioned.

In a case where p1 is 1, as the method for producing the compound (1),for example, the following methods (20) to (25) may be mentioned.

<Method (10)>

As the starting material, commercially available compound (10) is to beused.HO—CH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—CH₂—OH  (10)

In the presence of a basic compound, to the compound (10), A¹-O—CF═CF₂is reacted to obtain a mixture of compound (11), compounds (3A) andunreacted compound (10).A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—CH₂—OH  (11)A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—CH₂OCF₂CHF—O-A¹  (3A)

From the mixture, the compound (11) is isolated, and the compound (11)and CF₃CF₂CF₂OCF(CF₃)C(O)F are subjected to an esterification reactionto obtain compound (12). The esterification reaction may be a reactionof the compound (11) with other acid fluoride, acid chloride, acidbromide, acid anhydride or the like.A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—CH₂—OC(O)CF(CF₃)OCF₂CF₂CF₃  (12)

By using fluorine gas, hydrogen atoms in the compound (12) aresubstituted by fluorine atoms to obtain compound (13). The fluorinationstep may, for example, be carried out in accordance with the methoddescribed in WO2000/56694.A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)(CF₂CF₂O)—C(O)CF(CF₃)OCF₂CF₂CF₃  (13)

To the compound (13), an alcohol (methanol, ethanol, 1-propanol,2-propanol, etc.; hereinafter referred to as R¹⁰OH, where R¹⁰ is analkyl group) is reacted to obtain compound (14).A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)—CF₂—C(O)OR¹⁰  (14)

The compound (14) is subjected to hydrogen reduction by using a reducingagent (sodium borohydride, lithium aluminum hydride, etc.) to obtaincompound (15).A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)—CF₂—CH₂OH  (15)

In the presence of a basic compound, to the compound (15), CF₃SO₂Cl isreacted to obtain compound (16).A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)—CF₂—CH₂OSO₂CF₃  (16)

In the presence of a basic compound, to the compound (16),HOCH₂C(CH₂OCH₂CH═CH₂)₃ is reacted to obtain compound (17).A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)—CF₂—CH₂OCH₂—C(CH₂OCH₂CH═CH₂)₃  (17)

The compound (17) and HSiR¹³ _(n1)X¹ _(3-n1) are subjected to ahydrosilylation reaction to obtain compound (1A). The hydrosilylationreaction is preferably carried out by using a transition metal catalystsuch as platinum or a radical generator such as an organic peroxide.A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)—CF₂—CH₂OCH₂—C[CH₂OCH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1A)

Here, when the above formula is summarized in the order ofoxyfluoroalkylene units, the compound (1A) is represented by thefollowing formula.A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)(CF₂CH₂O)—CH₂C[CH₂OCH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1A)<Method (11)>

As the starting material, the compound (11) obtained in the method (10)is to be used.A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—CH₂—OH  (11)

In the presence of a basic compound, to the compound (11), CF₃SO₂Cl isreacted to obtain compound (16B).A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—CH₂OSO₂CF₃  (16B)

In the presence of a basic compound, to the compound (16B),HOCH₂C(CH₂OCH₂CH═CH₂)₃ is reacted to obtain compound (17B).A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—CH₂OCH₂—C(CH₂OCH₂CH═CH₂)₃  (17B)

The compound (17B) and HSiR¹³ _(n1)X¹ _(3-n1) are subjected to ahydrosilylation reaction to obtain compound (1B).A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—CH₂OCH₂—C[CH₂OCH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1B)

Here, when the above formula is summarized in the order ofoxyfluoroalkylene units, the compound (1B) is represented by thefollowing formula.A¹-O—(CHFCF₂O)(CH₂CF₂O)(R^(F1)O)_(x)(CF₂CH₂O)—CH₂—C[CH₂OCH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1B)<Method (12)>

As the starting material, compound (15C) obtained by the methoddescribed in WO2013/121984 is to be used.A¹-O—(R^(F1)O)_(x)-Q¹²-CH₂OH  (15C)wherein Q¹² is a perfluoroalkylene group having no branched structure.

In the presence of a basic compound, to the compound (15C), CF₃SO₂Cl isreacted to obtain compound (16C).A¹-O—(R^(F1)O)_(x)-Q¹²-CH₂OSO₂CF₃  (16C)

In the presence of a basic compound, to the compound (16C),HOCH₂C(CH₂OCH₂CH═CH₂)₃ is reacted to obtain compound (17C).A¹-O—(R^(F1)O)_(x)-Q¹²-CH₂OCH₂—C(CH₂OCH₂CH═CH₂)₃  (17C)

The compound (17C) and HSiR¹³ _(n1)X¹ _(3-n1) are subjected to ahydrosilylation reaction to obtain compound (1C).A¹-O—(R^(F1)O)_(x)-Q¹²-CH₂OCH₂—C[CH₂OCH₂CH₂CH₂—SiR¹³ _(n1)X¹_(3-n1)]₃  (1C)

Here, when the above formula is summarized in the order ofoxyfluoroalkylene units, the compound (1C) is represented by thefollowing formula.A¹-O—(R^(F1)O)_(x)(Q¹²CH₂O)—CH₂—C[CH₂OCH₂CH₂CH₂—SiR¹³ _(n1)X¹_(3-n1)]₃  (1C)<Method (13)>

HOCH₂C(CH₂CH═CH₂)₃ and (CF₃SO₂)₂O are reacted to obtain compound (20).CF₃SO₂OCH₂C(CH₂CH═CH₂)₃  (20)

As the starting material, the compound (15) obtained in the method (10)is to be used.A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)—CF₂—CH₂OH  (15)wherein x is an integer of from 1 to 198.

In the presence of a basic compound, the compound (20) is reacted to thecompound (15) to obtain compound (17D).A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)—CF₂—CH₂OCH₂—C(CH₂CH═CH₂)₃  (17D)

The compound (17D) and HSiR¹³ _(n1)X¹ _(3-n1) are subjected to ahydrosilylation reaction to obtain compound (1D).A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)—CF₂—CH₂OCH₂—C[CH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1D)

Here, when the above formula is summarized in the order ofoxyfluoroalkylene units, the compound (1D) is represented by thefollowing formula.A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)(CF₂CH₂O)—CH₂—C[CH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1D)<Method (14)>

As the starting material, the compound (11) obtained in the method (10)is to be used.A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—CH₂—OH  (11)

In the presence of a basic compound, to the compound (11), the compound(20) obtained in the method (13) is reacted to obtain compound (17E).A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—CH₂OCH₂—C(CH₂CH═CH₂)₃  (17E)

The compound (17E) and HSiR¹³ _(n1)X¹ _(3-n1) are subjected to ahydrosilylation reaction to obtain compound (1E).A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—CH₂OCH₂—C[CH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1E)

Here, when the above formula is summarized in the order ofoxyfluoroalkylene units, the compound (1E) is represented by thefollowing formula.A¹-O—(CHFCF₂O)(CH₂CF₂O)(R^(F1)O)_(x)(CF₂CH₂O)—CH₂—C[CH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1E)<Method (15)>

As the starting material, compound (15C) obtained by the methoddescribed in WO2013/121984 is to be used.A¹-O—(R^(F1)O)_(x)-Q¹²-CH₂OH  (15C)wherein Q¹² is a perfluoroalkylene group having no branched structure.

In the presence of a basic compound, to the compound (15C), the compound(20) obtained in the method (13) is reacted to obtain compound (17F).A¹-O—(R^(F1)O)_(x)-Q¹²-CH₂OCH₂—C(CH₂CH═CH₂)₃  (17F)

The compound (17F) and HSiR¹³ _(n1)X¹ _(3-n1) are subjected to ahydrosilylation reaction to obtain compound (1F).A¹-O—(R^(F1)O)_(x)-Q¹²-CH₂OCH₂—C[CH₂CH₂CH₂—SiR¹³ _(n1)X¹ _(3-n1)]₃  (1F)

Here, when the above formula is summarized in the order ofoxyfluoroalkylene units, the compound (1F) is represented by thefollowing formula.A¹-O—(R^(F1)O)_(x)(Q¹²CH₂O)—CH₂—C[CH₂CH₂CH₂—SiR¹³ _(n1)X¹_(3-n1)]₃  (1F)<Method (20)>

As the starting material, the compound (14) obtained in the method (10)is to be used.A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)—CF₂—C(O)OR¹⁰  (14)

To the compound (14), H₂N—R¹¹—C(CH₂CH═CH₂)₃ is reacted to obtaincompound (17G).A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)—CF₂—C(O)NH—R¹¹—C(CH₂CH═CH₂)₃  (17G)

The compound (17G) and HSiR¹³ _(n1)X¹ _(3-n1) are subjected to ahydrosilylation reaction to obtain compound (1G).A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)—CF₂—C(O)NH—R¹¹—C[CH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1G)<Method (21)>

As the starting material, the compound (11) obtained in the method (10)is to be used.A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—CH₂—OH  (11)

In accordance with the method described in J. Org. Chem., Vol. 64, 1999,p. 2564-2566, the compound (11) is oxidized to obtain compound (13H).A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—C(O)OH  (13H)

To the compound (13H), R¹⁰OH is reacted to obtain compound (14H).A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—C(O)OR¹⁰  (14H)

To the compound (14H), H₂N—R¹¹—C(CH₂CH═CH₂)₃ is reacted to obtaincompound (17H).A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—C(O)NH—R¹¹—C(CH₂CH═CH₂)₃  (17H)

The compound (17H) and HSiR¹³ _(n1)X¹ _(3-n1) are subjected to ahydrosilylation reaction to obtain compound (1H).A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—C(O)NH—R¹¹—C[CH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1H)

Here, when the above formula is summarized in the order ofoxyfluoroalkylene units, the compound (1H) is represented by thefollowing formula.A¹-O—(CHFCF₂O)(CH₂CF₂O)(R^(F1)O)_(x)—CF₂—C(O)NH—R¹¹—C[CH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1H)<Method (22)>

As the starting material, compound (14I) obtained by the methoddescribed in WO2013/121984 is to be used.A¹-O—(R^(F1)O)_(x)-Q¹²-C(O)OR¹⁰  (14I)wherein Q¹² is a perfluoroalkylene group having no branched structure.

To the compound (14I), H₂N—R¹¹—C(CH₂CH═CH₂)₃ is reacted to obtaincompound (17I).A¹-O—(R^(F1)O)_(x)-Q¹²-C(O)NH—R¹¹—C(CH₂CH═CH₂)₃  (17I)

The compound (17I) and HSiR¹³ _(n1)X¹ _(3-n1) are subjected to ahydrosilylation reaction to obtain compound (1I).A¹-O—(R^(F1)O)_(x)-Q¹²-C(O)NH—R¹¹—C[CH₂CH₂CH₂—SiR¹³ _(n1)X¹_(3-n1)]₃  (1I)<Method (23)>

CF₂═CFOCF₂CF₂CF₂—C(O)OCH₃ and H₂N—R¹¹—C(CH₂CH═CH₂)₃ are reacted toobtain compound (30).CF₂═CFOCF₂CF₂CF₂—C(O)NH—R¹¹—C(CH₂CH═CH₂)₃  (30)

As the starting material, the compound (15) obtained in the method (10)is to be used.A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)—CF₂—CH₂OH  (15)wherein x is an integer of from 1 to 198.

In the presence of a basic compound, the compound (30) is reacted to thecompound (15) to obtain compound (17J).A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)—CF₂CH₂OCF₂CHFOCF₂CF₂CF₂—C(O)NH—R¹¹—C(CH₂CH═CH₂)₃  (17J)

The compound (17J) and HSiR¹³ _(n1)X¹ _(3-n1) are subjected to ahydrosilylation reaction to obtain compound (1J).A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)—CF₂CH₂OCF₂CHFOCF₂CF₂CF₂—C(O)NH—R¹¹—C[CH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1J)

Here, when the above formula is summarized in the order ofoxyfluoroalkylene units, the compound (1J) is represented by thefollowing formula.A¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F1)O)_(x)(CF₂CH₂O)(CF₂CHFO)—CF₂CF₂CF₂—C(O)NH—R¹¹—C[CH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1J)<Method (24)>

As the starting material, the compound (11) obtained in the method (10)is to be used.A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂—CH₂OH  (11)

In the presence of a basic compound, to the compound (11), the compound(30) obtained in the method (23) is reacted to obtain compound (17K).A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂CH₂OCF₂CHFOCF₂CF₂CF₂—C(O)NH—R¹¹—C(CH₂CH═CH₂)₃  (17K)

The compound (17K) and HSiR¹³ _(n1)X¹ _(3-n1) are subjected to ahydrosilylation reaction to obtain compound (1K).A¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F1)O)_(x)—CF₂CH₂OCF₂CHFOCF₂CF₂CF₂—C(O)NH—R¹¹—C[CH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1K)

Here, when the above formula is summarized in the order ofoxyfluoroalkylene units, the compound (1K) is represented by thefollowing formula.A¹-O—(CHFCF₂O)(CH₂CF₂O)(R^(F1)O)_(x)(CF₂CH₂O)(CF₂CH₂O)—CF₂CF₂CF₂—C(O)NH—R¹¹—C[CH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1K)<Method (25)>

As the starting material, compound (15C) obtained by the methoddescribed in WO2013/121984 is to be used.A¹-O—(R^(F1)O)_(x)—R^(F)CH₂OH  (15C)wherein x is an integer of from 1 to 200, and R^(F) is aperfluoroalkylene group having no branched structure.

In the presence of a basic compound, to the compound (15C), the compound(30) obtained in the method (23) is reacted to obtain a compound (17L).A¹-O—(R^(F1)O)_(x)—R^(F)CH₂OCF₂CHFOCF₂CF₂CF₂—C(O)NH—R¹¹—C(CH₂CH═CH₂)₃  (17L)

The compound (17L) and HSiR¹³ _(n1)X¹ _(3-n1) are subjected to ahydrosilylation reaction to obtain compound (1L).A¹-O—(R^(F1)O)_(x)—R^(F)CH₂OCF₂CHFOCF₂CF₂CF₂—C(O)NH—R¹¹—C[CH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1L)

Here, when the above formula is summarized in the order ofoxyfluoroalkylene units, the compound (1L) is represented by thefollowing formula.A¹-O—(R^(F1)O)_(x)(R^(F)CH₂O)(CF₂CHFO)—CF₂CF₂CF₂—C(O)NH—R¹¹—C[CH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃  (1L)(The Present Compound)

The present compound may be a single compound composed of one type ofcompound (1), or a mixture composed of at least two types of compound(1) different in A¹, (R^(f1)O)_(m1), Q¹, R¹, p1, R¹¹, R¹², SiR¹³ _(n1)X¹_(3-n1), etc.

In the present invention, compound (1) being a single compound is meantfor the same group of compounds except having a distribution in thenumber of m1. For example, in the case of compound (1-1), when(R^(F1)O)_(m10) is {(CF₂O)_(m11)(CF₂CF₂O)_(m12)}, it is meant for thesame group of compounds except having a distribution in m11 and m12 andwhen represented by {(CF₂O)_(m11/m10)(CF₂CF₂O)_(m12/m10)}_(m10), it ismeant for the same group of compounds except having a distribution inthe number of m10. Since commercially available compound (10) is acompound which may normally be regarded as a single compound in theabove sense, its derivatives having no change occurred at the(R^(F1)O)_(x) portion can be regarded as a single compound so long asother portions (A¹, Q¹¹, Q¹², R¹, p1, R¹¹, R¹², SiR¹³ _(n1)X¹ _(3-n1),etc.) are the same.

The number average molecular weight of the present compound ispreferably from 500 to 20,000, more preferably from 800 to 10,000,particularly preferably from 1,000 to 8,000. When the number averagemolecular weight is within the range, abrasion resistance will beexcellent.

[Fluorinated Ether Composition]

The fluorinated ether composition of the present invention (hereinafterreferred to also as the present composition) is a composition comprisingcompound (1), and a fluorinated ether compound other than the compound(1). The fluorinated ether compound other than the compound (1)(hereinafter referred to also as other fluorinated ether compound) may,for example, be a fluorinated ether compound by-produced in the processfor producing the compound (1), a known (particularly commerciallyavailable) fluorinated ether compound to be used in the sameapplications as the compound (1), etc. Other fluorinated ether compoundis preferably a compound which is less likely to reduce the propertiesof the compound (1), and its relative content to the compound (1) in thepresent composition is preferably in such an amount as less likely toreduce the properties of the compound (1).

In a case where other fluorinated ether compound is a fluorinated ethercompound by-produced in the process for producing the compound (1), thepurification of the compound (1) in the production of the compound (1)becomes easy, and the purification process can be simplified. In a casewhere other fluorinated ether compound is a known fluorinated ethercompound to be used in the same applications as the compound (1), theremay be a case where a new function or effect such as to supplement theproperties of the compound (1) is exhibited.

Such other fluorinated ether compound is preferably at least one memberselected from the group consisting of the following fluorinated ethercompound (2), the following fluorinated ether compound (3) and thefollowing fluorinated ether compound (4).

Fluorinated ether compound (2): A fluorinated ether compound wherein inthe fluorinated ether compound represented by the formula (1), a grouphaving said —C[—R¹²—SiR¹³ _(n1)X¹ _(3-n1)]₃ is bonded to both sides ofsaid (R^(f1)O)_(m1),

Fluorinated ether compound (3): A fluorinated ether compound wherein inthe fluorinated ether compound represented by the formula (1), a grouphaving said A¹ is bonded to both sides of said (R^(f1)O)_(m1),

Fluorinated ether compound (4): A fluorinated ether compound wherein inthe fluorinated ether compound represented by the formula (1), said—C[—R¹²—SiR¹³ _(n1)X¹ _(3-n1)]₃ is substituted by —C[—R¹²SiR¹³ _(n1)X¹_(3-n1)]_(3-t)[—R¹⁵]_(t) (wherein R¹⁵ is an unsaturated bond-containinggroup which becomes —R¹²—SiR¹³ _(n1)X¹ _(3-n1) by addition of HSiR¹³_(n1)X¹ _(3-n1), or an isomer group of the unsaturated bond-containinggroup, and t is an integer of 1 to 3).

From such a viewpoint that it is less likely to reduce the properties ofthe compound (1), as the fluorinated ether compound (2), theafter-mentioned compound (2) is preferred, as the fluorinated ethercompound (3), the after-mentioned compound (3) is preferred, and as thefluorinated ether compound (4), the after-mentioned compound (4) ispreferred.

(Compound (2))

Compound (2) is a fluorinated ether compound represented by thefollowing formula (2).[X² _(3-n2)R²³_(n2)Si—R²²—]₃C—R²¹—[N(R²)C(O)]_(p2)—(R^(f2)O)_(m2)-Q²-[C(O)N(R²)]_(p2)—R²¹—C[—R²²—SiR²³_(n2)X² _(3-n2)]₃  (2)wherein R^(f2) is a fluoroalkylene group having no branched structure;m2 is an integer of from 2 to 210; (R^(f2)O)_(m2) may be one composed ofat least two types R^(f2)O different in number of carbon atoms; Q² is afluoroalkylene group having no branched structure; R² is a hydrogen atomor an alkyl group; p2 is 0 or 1, and two p2 may not be the same number;R²¹ is a single bond, an alkylene group, an alkylene group having anetheric oxygen atom at its terminal (which is the terminal on the sidebonded to [X² _(3-n2)R²³ _(n2)Si—R²²—]₃C), an alkylene group with atleast two carbon atoms having an etheric oxygen atom between itscarbon-carbon atoms, or an alkylene group with at least two carbon atomshaving an etheric oxygen atom between its carbon-carbon atoms and at itsterminal (which is the terminal on the side bonded to [X² _(3-n2)R²³_(n2)Si—R²²—]₃C), and two R²¹ may not be the same group; R²² is analkylene group, an alkylene group having an etheric oxygen atom at itsterminal (but excluding the terminal on the side bonded to Si), or analkylene group with at least two carbon atoms having an etheric oxygenatom between its carbon-carbon atoms; R²³ is a hydrogen atom or amonovalent hydrocarbon group; X² is a hydrolyzable group; n2 is aninteger of from 0 to 2; and six [—R²²—SiR²³ _(n2)X² _(3-n2)] may not beall the same group.

(R^(f2)O)_(m2), Q², R², p2, R²¹, R²² and SiR²³ _(n2)X² _(3-n2) may,respectively, be the same as (R^(f1)O)_(m1), Q¹, R¹, p1, R¹¹, R¹² andSiR¹³ _(n1)X¹ _(3-n1) in compound (1), and their preferred examples arealso the same.

In a case where p2 is 0 and R^(f2) is a fluoroalkylene group containingat least two hydrogen atoms and having no branched structure, andfurther, no etheric oxygen atom exists at the terminal of R²¹ on theside bonded to R^(f2), at least one fluorine atom is bonded to thecarbon atom at the terminal of R^(f2) on the side bonded to R²¹.

In a case where p2 is 0 and Q² is a fluoroalkylene group containing atleast two hydrogen atoms and having no branched structure, and further,no etheric oxygen atom exists at the terminal of R²¹ on the side bondedto Q², at least one fluorine atom is bonded to the carbon atom at theterminal of Q² on the side bonded to R²¹.

(Preferred Form of Compound (2))

As the compound (2), from such a viewpoint that the surface layer willbe further excellent in abrasion resistance and fingerprint stainremovability, compound (2-1) is preferred.[X² _(3-n2)R²³_(n2)Si—R²²—]₃C—R²¹—[N(R²)C(O)]_(p2)-Q²¹-(R^(F2)O)_(m20)-Q²²-[C(O)N(R²)]_(p2)—R²¹—C[—R²²—SiR²³_(n2)X² _(3-n2)]₃  (2-1)wherein R², p2, R²¹, R²², R²³, X² and n2 are the same as in the aboveformula (2); Q²¹ is a single bond, a fluoroalkylene group containing atleast one hydrogen atom and having no branched structure, afluoroalkylene group containing at least one hydrogen atom and having nobranched structure, which has an etheric oxygen atom at its terminal(but excluding the terminal on the side bonded to C(O)), afluoroalkylene group with at least two carbon atoms containing at leastone hydrogen atom and having no branched structure, which has an ethericoxygen atom between its carbon-carbon atoms, or a fluoroalkylene groupwith at least two carbon atoms containing at least one hydrogen atom andhaving no branched structure, which has an etheric oxygen atom betweenits carbon-carbon atoms and at its terminal (but excluding the terminalon the side bonded to C(O)) (provided that the number of oxygen atoms isat most 10); R^(F2) is a perfluoroalkylene group having no branchedstructure; m20 is an integer of from 2 to 200; (R^(F2)O)_(m20) may beone composed of at least two types of R^(F2)O different in number ofcarbon atoms; Q²² is a perfluoroalkylene group having no branchedstructure, a fluoroalkylene group containing at least one hydrogen atomand having no branched structure, or a fluoroalkylene group with atleast two carbon atoms containing at least one hydrogen atom and havingno branched structure, which has an etheric oxygen atom between itscarbon-carbon atoms.

Q²¹, (R^(F2)O)_(m20) and Q²² may, respectively, be the same as Q¹¹,(R^(F1)O)_(m10) and Q¹² in the compound (1-1), and their preferredexamples are also the same.

In a case where Q²¹ is a fluoroalkylene group containing at least onehydrogen atom and having no branched structure, or a fluoroalkylenegroup with at least two carbon atoms containing at least one hydrogenatom and having no branched structure, which has an etheric oxygen atombetween its carbon-carbon atoms, and no etheric oxygen atom exists atthe terminal of Q²¹ on the side bonded to (R^(F2)O)_(m20), at least onehydrogen atom is bonded to the carbon atom at the terminal of Q²¹ on theside bonded to (R^(F2)O)_(m20).

(Method for Producing Compound (2))

In a case where p2 is 0, as the method for producing the compound (2),for example, the following methods (30) and (31) may be mentioned.

In a case where p2 is 1, as the method for producing the compound (2),for example, the following methods (40) and (41) may be mentioned.

<Method (30)>

As the starting material, commercially available compound (10) is to beused.HO—CH₂—CF₂O(R^(F2)O)_(x)—CF₂—CH₂—OH  (10)wherein x is an integer of from 1 to 199.

In the presence of a basic compound, to the compound (10), CF₃SO₂Cl isreacted to obtain compound (18).CF₃SO₂OCH₂—(CF₂O)(R^(F2)O)_(x)—CF₂—CH₂OSO₂CF₃  (18)

In the presence of a basic compound, to the compound (18),HOCH₂C(CH₂OCH₂CH═CH₂)₃ is reacted to obtain compound (19).(CH₂═CHCH₂OCH₂)₃C—CH₂OCH₂—(CF₂O)(R^(F2)O)_(x)—CF₂—CH₂OCH₂—C(CH₂OCH₂CH═CH₂)₃  (19)

The compound (19) and HSiR²³ _(n2)X² _(3-n2) are subjected to ahydrosilylation reaction to obtain compound (2A).[X² _(3-n2)R²³_(n2)Si—CH₂CH₂CH₂OCH₂]₃C—CH₂OCH₂—(CF₂O)(R^(F2)O)_(x)—CF₂—CH₂OCH₂—C[CH₂OCH₂CH₂CH₂—SiR²³ _(n2)X² _(3-n2)]₃  (2A)<Method (31)>

As the starting material, commercially available compound (10) is to beused.HO—CH₂—(CF₂O)(R^(F2)O)_(x)—CF₂—CH₂—OH  (10)wherein x is an integer of from 1 to 199.

In the presence of a basic compound, to the compound (10), the compound(20) obtained in the method (13) is reacted to obtain compound (19B).(CH₂═CHCH₂)₃C—CH₂OCH₂—(CF₂O)(R^(F2)O)_(x)—CF₂—CH₂OCH₂—C(CH₂CH═CH₂)₃  (19B)

The compound (19B) and HSiR²³ _(n2)X² _(3-n2) are subjected to ahydrosilylation reaction to obtain compound (2B).[X² _(3-n2)R²³_(n2)Si—CH₂CH₂CH₂]₃C—CH₂OCH₂—(CF₂O)(R^(F2)O)_(x)—CF₂—CF₂OCH₂—C[CH₂CH₂CH₂—SiR²³_(n2)X² _(3-n2)]₃  (2B)<Method (40)>

As the starting material, commercially available compound (10) is to beused.HO—CH₂—CF₂O(R^(F2)O)_(x)—CF₂—CH₂—OH  (10)wherein x is an integer of from 1 to 199.

In accordance with the method described in J. Org. Chem., Vol. 64, 1999,p. 2564-2566, the compound (10) is oxidized to obtain compound (25).HOC(O)—(CF₂O)(R^(F2)O)_(x)—CF₂—C(O)OH  (25)

To the compound (25), R¹⁰OH is reacted to obtain compound (26).R¹⁰OC(O)—(CF₂O)(R^(F2)O)_(x)—CF₂—C(O)OR¹⁰  (26)

To the compound (26), H₂N—R²¹—C(CH₂CH═CH₂)₃ is reacted to obtaincompound (27).(CH₂═CHCH₂)₃C—R²¹—NHC(O)—(CF₂O)(R^(F2)O)_(x)—CF₂—C(O)NH—R²¹—C(CH₂CH═CH₂)₃  (27)

The compound (27) and HSiR²³ _(n2)X² _(3-n2) are subjected to ahydrosilylation reaction to obtain compound (2C).[X² _(3-n2)R²³_(n2)Si—CH₂CH₂CH₂]₃C—R²¹—NHC(O)—(CF₂O)(R^(F2)O)_(x)—CF₂—C(O)NH—R²¹—C[CH₂CH₂CH₂—SiR²³_(n2)X² _(3-n2)]₃  (2C)<Method (41)>

As the starting material, commercially available compound (10) is to beused.HOCH₂—(CF₂O)(R^(F2)O)_(x)—CF₂—CH₂OH  (10)wherein x is an integer of from 1 to 199.

In the presence of a basic compound, to the compound (10), the compound(30) obtained in the method (23) is reacted to obtain compound (27D).(CH₂═CHCH₂)₃C—R²¹—NHC(O)—CF₂CF₂CF₂OCHFCF₂OCH₂—(CF₂O)(R^(F2)O)_(x)—CF₂CH₂OCF₂CHFOCF₂CF₂CF₂—C(O)NH—R²¹—C(CH₂CH═CH₂)₃  (27D)

The compound (27D) and HSiR²³ _(n2)X² _(3-n2) are subjected to ahydrosilylation reaction to obtain compound (2D).[X² _(3-n2)R²³_(n2)Si—CH₂CH₂CH₂]₃C—R²¹—NHC(O)—CF₂CF₂CF₂OCHFCF₂OCH₂—(CF₂O)(R^(F2)O)_(x)—CF₂CH₂OCF₂CHFOCF₂CF₂CF₂—C(O)NH—R²¹—C[CH₂CH₂CH₂—SiR²³_(n2)X² _(3-n2))₃  (2D)(Compound (3))

Compound (3) is a fluorinated ether compound represented by thefollowing formula (3).A³¹-O—(R^(f3)O)_(m3)-A³²  (3)wherein A³¹ and A³² are each independently a C₁₋₂₀ perfluoroalkyl group;R^(f3) is a fluoroalkylene group having no branched structure; m3 is aninteger of from 2 to 210; and (R^(f3)O)_(m3) may be one composed of atleast two types of R^(f3)O different in number of carbon atoms.

A³¹, (R^(f3)O)_(m3) and A³² may, respectively, be the same as A¹,(R^(f1)O)_(m1) and A¹ in the compound (1), and their preferred examplesare also the same. From such a viewpoint that a compound to beby-produced during the production of the compound (1) can be effectivelyutilized, they are, respectively, preferably the same as A¹,(R^(f1)O)_(m1) and A¹ in the compound (1).

(Preferred Form of Compound (3))

As the compound (3), from such a viewpoint that the surface layer willbe further excellent in abrasion resistance and fingerprint stainremovability, compound (3-1) is preferred.A³¹-O-Q³¹-(R^(F3)O)_(m30)-[Q³²-O]_(p3)-A³²  (3-1)wherein A³¹ and A³² are each independently a C₁₋₂₀ perfluoroalkyl group;Q³¹ is a single bond, a fluoroalkylene group containing at least onehydrogen atom and having no branched structure, a fluoroalkylene groupcontaining at least one hydrogen atom and having no branched structure,which has an etheric oxygen atom at its terminal (but excluding theterminal on the side bonded to A³¹-O), a fluoroalkylene group with atleast two carbon atoms containing at least one hydrogen atom and havingno branched structure, which has an etheric oxygen atom between itscarbon-carbon atoms, or a fluoroalkylene group with at least two carbonatoms containing at least one hydrogen atom and having no branchedstructure, which has an etheric oxygen atom between its carbon-carbonatoms and at its terminal (but excluding the terminal on the side bondedto A³¹-O) (provided that the number of oxygen atoms is at most 10); Q³²is a fluoroalkylene group containing at least one hydrogen atom andhaving no branched structure, or a fluoroalkylene group with at leasttwo carbon atoms containing at least one hydrogen atom and having nobranched structure, which has an etheric oxygen atom between itscarbon-carbon atoms (provided that the number of oxygen atoms is at most10); R^(F3) is a perfluoroalkylene group having no branched structure;m30 is an integer of from 2 to 200; (RF³O)_(m30) may be one composed ofat least two types of R^(F3)O different in number of carbon atoms; p3 is0 when Q³¹ is a single bond, and 1 when Q³¹ is other than a single bond.

A³¹, Q³¹, (RF³O)_(m30), Q³² and A³² may, respectively, be the same asA¹, Q¹¹, (R^(F1)O)_(m10), Q¹¹ (but excluding a single bond) and A¹ inthe compound (1-1), and their preferred examples are also the same. Fromsuch a viewpoint that a compound to be by-produced during the productionof the compound (1-1) can be effectively utilized, they are preferablythe same as A¹, Q¹¹, (R^(F1)O)_(m10), Q¹¹ (but excluding a single bond)and A¹ in the compound (1-1).

In a case where Q³¹ is a fluoroalkylene group containing at least onehydrogen atom and having no branched structure, or a fluoroalkylenegroup with at least two carbon atoms containing at least one hydrogenatom and having no branched structure, which has an etheric oxygen atombetween its carbon-carbon atoms, and no etheric oxygen atom is presentat the terminal of Q³¹ on the side bonded to (R^(F3)O)_(m30), at leastone hydrogen atom is bonded to the carbon atom at the terminal of Q³¹ onthe side bonded to (R^(F3)O)_(m30).

(Method for Producing Compound (3))

As the method for producing the compound (3), for example, the followingmethods (50) and (51) may be mentioned.

<Method (50)>

The compound (3A) is isolated from a mixture of the compound (11), thecompound (3A) and unreacted compound (10) obtained in the method (10).A³¹-O—CHFCF₂OCH₂—(CF₂O)(R^(F3)O)_(x)—CF₂—CH₂OCF₂CHF—O-A³²  (3A)<Method (51)>

The compound (3A) is fluorinated by fluorine gas to obtain compound(3B).A³¹-O—(CF₂CF₂O)(CF₂CF₂O)(R^(F3)O)_(x)(CF₂CF₂O)(CF₂CF₂O)-A³²  (3B)

As the compound (3) wherein Q³¹ is a single bond and p3 is 0, acommercially available product may be used. As the commerciallyavailable product, FOMBLIN (registered trademark) M, FOMBLIN (registeredtrademark) Y, FOMBLIN (registered trademark) Z (manufactured by SolvaySolexis), Krytox (registered trademark) (manufactured by DuPont), Demnum(registered trademark) (manufactured by Daikin Industries, Ltd.), etc.may be mentioned.

The compound (4) is a compound wherein in the compound (1),—C[—R¹²—SiR¹³ _(n1)X¹ _(3-n1)]₃ is substituted by —C[—R¹²—SiR¹³ _(n1)X¹_(3-n1)]_(3-t)[—R¹⁵]_(t), and it is the same compound as the compound(1) except for the portion —C[—R¹²—SiR¹³ _(n1)X¹_(3-n1)]_(3-t)[—R¹⁵]_(t). R¹⁵ is a group which becomes [—R¹²—SiR¹³_(n1)X¹ _(3-n1)] by a hydrosilylation reaction, or its isomer group, andt is an integer of from 1 to 3.

As described above, [—R¹²—SiR¹³ _(n1)X¹ _(3-n1)] is formed by ahydrosilylation reaction wherein HSiR¹³ _(n1)X¹ _(3-n1) is added to analkenyl moiety having an unsaturated group at the terminal. For example,by adding HSiR¹³ _(n1)X¹ _(3-n1) to —C(CH₂CH═CH₂)₃, —C[—CH₂CH₂CH₂—SiR¹³_(n1)X¹ _(3-n1)]₃ will be formed. In this case, (CH₂CH═CH₂) is R¹⁵. Inthe hydrosilylation reaction, there may be a case where a side reactiontakes place to form an alkenyl group so-called an inner olefin, whereina terminal unsaturated group of R¹⁵ is isomerized to a non-terminalposition. For example, —CH₂CH═CH₂ may be isomerized to —CH═CHCH₃. Thealkenyl group portion having an unsaturated group at a non-terminalposition will remain without reacting with HSiR¹³ _(n1)X¹ _(3-n1).

In the hydrosilylation reaction in the production of the compound (1),when R¹⁵ remains as unreacted, or when R¹⁵ is isomerized, a compoundwill be by-produced wherein its terminal is —C[—R¹²—SiR¹³ _(n1)X¹_(3-n1)]_(3-t)[—R¹⁵]_(t), and this compound is compound (4).

(Composition of the Present Composition)

The total proportion of the present compound and other fluorinated ethercompound in the present composition is preferably 80 to 100 mass %,particularly preferably 85 to 100 mass %. That is, the proportion ofimpurities is preferably at most 20 mass %, particularly preferably atmost 15 mass %. When the proportion of the present compound and otherfluorinated ether compound is within the above range, the surface layerwill be excellent in water/oil repellency, abrasion resistance,fingerprint stain removability, lubricity and outer appearance.

The proportion of other fluorinated ether compound to the total of thepresent compound and other fluorinated ether compound is preferably morethan 0 mass % and less than 40 mass %, more preferably more than 0 mass% and at most 30 mass %, particularly preferably more than 0 mass % andat most 20 mass %. That is, the proportion of the present compound ispreferably more than 60 mass % and less than 100 mass %, more preferablyat least 70 mass % and less than 100 mass %, particularly preferably atleast 80 mass % and less than 100 mass %. When the proportions of thepresent compound and other fluorinated ether compound are within theabove ranges, the surface layer will be excellent in water/oilrepellency, abrasion resistance, fingerprint stain removability,lubricity and outer appearance.

Here, in a case where at least one member selected from the compound(2), the compound (3) and the compound (4) is contained as said otherfluorinated ether compound, the composition of the present compositionwill be as follows.

In the present ether composition, the total proportion of the presentcompound, the compound (2), the compound (3) and the compound (4) ispreferably more than 60 mass % and at most 100 mass %, more preferablyfrom 70 to 100 mass %, particularly preferably from 80 to 100 mass %.That is, the total proportion of impurities and fluorinated ethercompounds other than the present compound, the compound (2), thecompound (3) and the compound (4) is preferably less than 40 mass %,more preferably at most 30 mass %, particularly preferably at most 20mass %.

The proportion of the compound (2) to the total of the present compound,the compound (2), the compound (3) and the compound (4), is preferablymore than 0 mass % and less than 40 mass %, more preferably from 0 to 30mass %, particularly preferably from 0 to 20 mass %. The proportions ofthe compound (3) and the compound (4) are also similar to the proportionof the compound (2).

However, the total proportion of the compound (2), the compound (3) andthe compound (4), to the total of the present compound, the compound(2), the compound (3) and the compound (4), is preferably more than 0mass % and less than 40 mass %, particularly preferably more than 0 mass% and at most 30 mass %.

In a case where at least one member selected from the compound (2), thecompound (3) and the compound (4) is contained as other fluorinatedether compound, when the composition of the present composition iswithin the above range, the surface layer will be excellent in water/oilrepellency, abrasion resistance, fingerprint stain removability,lubricity and outer appearance.

The present compositions may contain impurities other than the presentcompound and other fluorinated ether compound. As impurities other thanthe present compound and other fluorinated ether compound, unavoidablecompounds, etc. in the production of the present compound and otherfluorinated ether compound, may be mentioned. The present compositiondoes not contain a liquid state liquid medium which will be describedlater.

[Coating Liquid]

The coating liquid of the present invention (hereinafter referred toalso as the present coating liquid) comprises the present compound orpresent composition and a liquid medium. The coating liquid may be anyliquid and may be a solution or a dispersion.

The present coating liquid may be one which contains the presentcompound or the present composition and may contain impurities such asby-products, etc. formed in the process for producing the presentcompound.

The concentration of the present compound or the present composition ispreferably from 0.001 to 10 mass %, particularly preferably from 0.1 to1 mass %, in the coating liquid.

The liquid medium is preferably an organic solvent. The organic solventmay be fluorinated organic solvent or a non-fluorinated organic solvent,or may contain both solvents.

The fluorinated organic solvent may, for example, be a fluorinatedalkane, a fluorinated aromatic compound, a fluoroalkyl ether, afluorinated alkylamine, a fluoroalcohol, etc.

As the fluorinated alkane, a compound having from 4 to 8 carbon atoms ispreferred. Commercially available products may, for example, be C₆F₁₃H(manufactured by Asahi Glass Company, Limited, ASAHIKLIN (registeredtrademark) AC-2000), C₆F₁₃C₂H₅ (manufactured by Asahi Glass Company,Limited, ASAHIKLIN (registered trademark) AC-6000), C₂F₅CHFCHFCF₃(manufactured by Chemours, Vertrel (registered trademark) XF), etc.

As the fluorinated aromatic compound, for example, hexafluorobenzene,trifluoromethylbenzene, perfluorotoluene, bis(trifluoromethyl)benzene,etc. may be mentioned.

As the fluoroalkyl ether, a compound having from 4 to 12 carbon atoms ispreferred. Commercially available products may, for example, beCF₃CH₂OCF₂CF₂H (manufactured by Asahi Glass Company, Limited, ASAHIKLIN(registered trademark) AE-3000), C₄F₉OCH₃ (manufactured by 3M, Novec(registered trademark) 7100), C₄F₉OC₂H₅ (manufactured by 3M, Novec(registered trademark) 7200), C₂F₅CF(OCH₃)C₃F₇ (manufactured by 3M,Novec (registered trademark) 7300), etc.

As the fluorinated alkyl amine, for example, perfluorotripropylamine,perfluorotributylamine, etc. may be mentioned.

As the fluoroalcohol, for example, 2,2,3,3-tetrafluoropropanol,2,2,2-trifluoroethanol, hexafluoroisopropanol, etc. may be mentioned.

As the non-fluorinated organic solvent, a compound consisting of onlyhydrogen and carbon atoms, or a compound consisting of only hydrogen,carbon and oxygen atoms, is preferred, and a hydrocarbon-type organicsolvent, an alcohol-type organic solvent, a ketone-type organic solvent,an ether-type organic solvent or an ester-type organic solvent may bementioned.

The present coating liquid contains the liquid medium in an amount ofpreferably from 90 to 99.999 mass %, particularly preferably from 99 to99.9 mass %.

The present coating liquid may contain, in addition to the presentcompound and the liquid medium, other components in a range not toimpair the effects of the present invention.

Other components may, for example, be known additives such as acidcatalysts or basic catalysts for promoting hydrolysis and condensationreaction of hydrolyzable silyl groups.

In the present coating liquid, the proportion of such other componentsis preferably at most 10 mass %, particularly preferably at most 1 mass%.

The solid content concentration in the present coating liquid ispreferably from 0.001 to 10 mass %, particularly preferably from 0.01 to1 mass %. The solid content concentration in the coating liquid is avalue calculated from the mass of the coating liquid before heating andthe mass after heating for 4 hours at 120° C. in a convection dryer. Theconcentration of the present composition can be calculated from thesolid content concentration, and the charged amounts of the presentcomposition and the solvent, etc.

[Article]

The article of the present invention has a surface layer formed of thepresent compound or the present composition at the surface of asubstrate.

(Surface Layer)

In the present compound or the present composition, silanol groups(Si—OH) are formed by a hydrolysis reaction of hydrolyzable silyl groups(SiR¹³ _(n1)X¹ _(3-n1)) in the present compound, and such silanol groupsare intermolecularly reacted to form Si—O—Si bonds, or such silanolgroups undergo a dehydration condensation reaction with hydroxy groups(substrate-OH) on the surface of a substrate to form chemical bonds(substrate-O—Si). That is, the surface layer in the present inventioncontains the present compound in such a state that part or all ofhydrolyzable silyl groups in the present compound underwent a hydrolysisreaction.

The thickness of the surface layer is preferably from 1 to 100 nm,particularly preferably from 1 to 50 nm. When the thickness of thesurface layer is at least the lower limit in the above range, the effectby surface treatment tends to be sufficiently obtained. When thethickness of the surface layer is at most the upper limit value in theabove range, utilization efficiency will be high. The thickness of thesurface layer can be calculated from the oscillation period of aninterference pattern of reflected X-ray by obtaining the interferencepattern of the reflected X-ray by means of an X-ray diffractometer forthin film analysis (manufactured by Rigaku Corporation, ATX-G).

(Substrate)

The substrate in the present invention is not particularly limited aslong as it is a substrate which is required to have water/oil repellencyimparted. The material for the substrate may, for example, be a metal, aresin, glass, sapphire, ceramic, stone, or a composite material thereof.The glass may have been chemically strengthened. The substrate may haveits surface treated with e.g. SiO₂.

As the substrate, a substrate for a touch panel, or a substrate fordisplay, is preferred, and a substrate for a touch panel is particularlypreferred. The substrate for a touch panel has a light-transmittingproperty. “Having a light-transmitting property” means that the verticalincidence type visible light transmittance in accordance with JIS R3106: 1998 (ISO 9050: 1990) is at least 25%. As the material for thetouch panel substrate, glass or a transparent resin is preferred.

(Method of Producing Article)

The article of the present invention may be produced, for example, bythe following methods.

A method of treating the surface of a substrate by a dry coating methodusing the present compound or the present composition, to obtain anarticle of the present invention.

A method of applying the present coating liquid to the surface of asubstrate by a wet coating method, followed by drying to obtain anarticle of the present invention.

<Dry Coating Method>

The present compound and the present compositions can be used as theyare in a dry coating method. The present compound and the presentcomposition are suitable for forming a surface layer excellent inadhesion by a dry coating method. As the dry coating method, a method ofe.g. vacuum deposition, CVD or sputtering may be mentioned. From theviewpoint of suppressing the decomposition of the present compound andfrom the viewpoint of simplicity of apparatus, a vacuum depositionmethod can be suitably used.

<Wet Coating Method>

As the wet coating method, a spin coating method, a wipe coating method,a spray coating method, a squeegee coating method, a dip coating method,a die coating method, an ink-jet method, a flow coating method, a rollcoating method, a casting method, a Langmuir-Blodgett method, a gravurecoating method, etc. may be mentioned.

<Post-Treatment>

In order to improve the abrasion resistance of the surface layer, as thecase requires, an operation to promote the reaction between the presentcompound and the substrate may be carried out. As such an operation,heating, humidification, light irradiation, etc. may be mentioned. Forexample, by heating the substrate having a surface layer formed, in anatmosphere having moisture, it is possible to accelerate a reaction suchas a hydrolysis reaction of hydrolyzable silyl groups to silanol groups,a reaction of silanol groups with hydroxy groups at the surface of thesubstrate, or a condensation reaction of silanol groups to form siloxanebonds.

After the surface treatment, among compounds in the surface layer, othercompounds or compounds not chemically bonded to the substrate may beremoved as the case requires. As a specific method, for example, amethod of letting a solvent flow on the surface layer, or a method ofwiping the surface layer with a cloth soaked with a solvent, may bementioned.

EXAMPLES

Now, the present invention will be described in further detail withreference to Examples, but the present invention is not limited to theseExamples.

Hereinafter, “%” is “mass %” unless otherwise specified. Further, amixture made of at least two types of compound (1) will be referred toas a “compound” and one made of compound (1) and other fluorinated ethercompound will be referred to as a “composition”.

Ex. 1 to 6, 11 to 16, 17 to 22, 27 to 36, 38 to 41, 43 to 45 and 48 to53 are Examples of the present invention, and Ex. 7 to 10, 23 to 26, 37,42, 46 and 47 are Comparative Examples.

Ex. 1: Production of Compound (1A-1) and Compound (3A-1) Ex. 1-1

Into a 300 mL three-necked flask, 24.4 g of a 24% KOH aqueous solution,33 g of tert-butyl alcohol, 220 g of compound (10-1) (manufactured bySolvay Solexis, FLUOROLINK (registered trademark) D4000) were put, and19.4 g of CF₃CF₂CF₂—O—CF═CF₂ (manufactured by Tokyo Chemical IndustryCo., Ltd.) was added. Under a nitrogen atmosphere, the mixture wasstirred at 60° C. for 8 hours. After washing it once with dilute aqueoushydrochloric acid, the organic phase, was collected and concentrated byan evaporator to obtain 233 g of crude product (a). The crude product(a) was fractionated by developing it by silica gel columnchromatography. As the developing solvents, C₆F₁₃CH₂CH₃ (manufactured byAsahi Glass Company, Limited, AC-6000), AC-6000/CF₃CH₂OCF₂CF₂H(manufactured by Asahi Glass Company, Limited, AE-3000)=½ (mass ratio)and AE-3000/ethyl acetate=9/1 (mass ratio) were used in this order. Withrespect to each fraction, the structures of terminal groups and the meanvalues of unit numbers (x1, x2) of structural units were obtained fromthe integral values of ¹H-NMR and ¹⁹F-NMR. It was found that in thecrude product (a), compound (11-1), compound (3A-1) and compound (10-1)were contained in amounts of 42 mol %, 49 mol % and 9 mol %,respectively. 98.6 g (yield: 44.8%) of compound (11-1) and 51.9 g(yield: 23.6%) of compound (3A-1) were obtained.HO—CH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂—OH  (10-1)CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂—OH  (11-1)CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CF₂—CH₂OCF₂CHF—O—CF₂CF₂CF₃  (3A-1)

NMR spectrum of compound (11-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.9 (2H),4.2 (2H), 5.8 to 6.0 (1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.8 (42F), −78.8 (1F), −80.8 (1F), −81.4 (1F), −82.2 (3F), −83.5 (1F),−85.3 to −88.2 (2F), −89.4 to −91.1 (82F), −130.5 (2F), −145.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of compound (1I-1): 4,150.

NMR spectrum of compound (3A-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 4.2 (4H),5.8 to 6.0 (2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.8 (42F), −78.8 (2F), −80.7 (2F), −82.2 (6F), −85.3 to −88.2 (4F),−89.4 to −91.1 (84F), −130.5 (4F), −145.1 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of compound (3A-1): 4,420.

Ex. 1-2

Into a 100 mL eggplant flask, 30.0 g of compound (11-1), 0.9 g of sodiumfluoride powder and 30 g of dichloropentafluoropropane (manufactured byAsahi Glass Company, Limited, AK-225) were put, and 3.5 g ofCF₃CF₂CF₂OCF(CF₃)C(O)F was added. Under a nitrogen atmosphere, themixture was stirred at 50° C. for 24 hours. After removal of sodiumfluoride powder by a pressure filter, excess CF₃CF₂CF₂OCF(CF₃)C(O)F andAK-225 were distilled off under reduced pressure. The obtained crudeproduct was diluted with C₆F₁₃H (manufactured by Asahi Glass Company,Limited, AC-2000), and passed through a silica gel column, whereupon therecovered solution was concentrated by an evaporator, to obtain 31.8 g(yield: 98.8%) of compound (12-1).CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂—OC(O)CF(CF₃)OCF₂CF₂CF₃  (12-1)

NMR spectrum of compound (12-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 4.2 (2H),4.7 (2H), 5.8 to 6.0 (1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.8 (42F), −78.8 to −88.2 (17F), −89.4 to −91.1 (82F), −130.3 (2F),−130.5 (2F), −132.5 (1F), −145.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of compound (12-1): 4,460.

Ex. 1-3

At a gas outlet of a 1 L nickel autoclave, a cooler maintained at 20°C., a NaF pellet packed layer and a cooler maintained at 0° C. wereinstalled in series. A liquid returning line to return a liquidcollected from the cooler maintained at 0° C. to the autoclave, wasinstalled.

Into the autoclave, 750 g of ClCF₂CFClCF₂OCF₂CF₂Cl (hereinafter referredto also as CFE-419) was put and stirred while maintaining thetemperature at 25° C. After blowing nitrogen gas into the autoclave at25° C. for 1 hour, 20% fluorine gas was blown at 25° C. for one hour ata flow rate of 2.0 L/hour. While blowing 20% fluorine gas at the sameflow rate, a solution prepared by dissolving 31.0 g of compound (12-1)in 124 g of CFE-419 was injected into the autoclave over a period of 4.3hours. While blowing 20% fluorine gas at the same flow rate, theinternal pressure of the autoclave was raised to 0.15 MPa (gaugepressure). Into the autoclave, 4 mL of a benzene solution containing0.05 g/mL of benzene in CFE-419, was injected while heating to 40° C.from 25° C., and then the benzene solution inlet of the autoclave wasclosed. After stirring for 15 minutes, 4 mL of the benzene solution wasinjected again while maintaining the temperature at 40° C., and then theinlet was closed. The same operation was repeated three more times. Thetotal amount of benzene injected was 0.17 g. While blowing 20% fluorinegas at the same flow rate, stirring was continued for 1 hour. Thepressure in the autoclave was set at atmospheric pressure, and nitrogengas was blown in for 1 hour. The content of the autoclave wasconcentrated by an evaporator to obtain 31.1 g (yield: 98.5%) ofcompound (13-1).CF₃CF₂CF₂—O—(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}(CF₂CF₂O)—C(O)CF(CF₃)OCF₂CF₂CF₃  (13-1)

NMR spectrum of compound (13-1);

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.7 (42F), −78.8 to −88.1 (11F), −89.4 to −91.1 (92F), −91.5 (2F),−130.3 (2F), −130.5 (2F), −132.5 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of compound (13-1): 4,550.

Ex. 1-4

Into a round bottom flask made of a tetrafluoroethylene-perfluoro(alkoxyvinyl ether) copolymer (hereinafter referred to also as PFA), 30.0 g ofcompound (13-1) and 60 g of AK-225 were put. The mixture was stirredwhile cooling in an ice bath, and under a nitrogen atmosphere, 2.0 g ofmethanol was dropwise slowly added from a dropping funnel. Whilebubbling with nitrogen, the mixture was stirred for 12 hours. Thereaction mixture was concentrated by an evaporator to obtain 27.6 g(yield: 98.8%) of compound (14-1).CF₃CF₂CF₂—O—(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—C(O)OCH₃  (14-1)

NMR spectrum of compound (14-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.9 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): —52.4 to−55.8 (42F), —82.2 (3F), —89.4 to −91.1 (92F), —30.5 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (14-1): 4,230.

Ex. 1-5

In a 100 mL three-necked eggplant flask, 0.18 g of lithium chloride wasdissolved in 18.3 g of ethanol. 25.0 g of the compound (14-1) was addedthereto, and while cooling in an ice bath, a solution prepared bydissolving 0.75 g of sodium borohydride in 22.5 g of ethanol, wasdropwise slowly added. The ice bath was removed, and stirring wascontinued while slowly warming to room temperature. After stirring for12 hours at room temperature, aqueous hydrochloric acid was dropwiseadded until the liquid became acidic. 20 mL of AC-2000 was added,followed by washing once with water and once with saturated brine,whereupon the organic phase was collected. The collected organic phasewas concentrated by an evaporator to obtain 24.6 g (yield: 99.0%) ofcompound (15-1).CF₃CF₂CF₂—O—(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OH  (15-1).

NMR spectrum of compound (15-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.9 (2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.7 (42F), −81.4 (1F), −82.2 (3F), −83.4 (1F), −89.4 to −91.1 (90F),−130.5 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (15-1): 4,200.

Ex. 1-6

Into a 100 mL two-necked eggplant flask, 20.0 g of the compound (15-1),20.0 g of 1,3-bis(trifluoromethyl)benzene (manufactured by TokyoChemical Industry Co., Ltd.), 1.01 g of CF₃SO₂Cl (manufactured by WakoPure Chemical Industries, Ltd.) and 1.00 g of triethylamine were put,and stirred at room temperature for 4 hours under a nitrogen atmosphere.After completion of the reaction, 15 g of AK-225 was added, followed bywashing once with each of water and saturated brine, whereupon theorganic phase was collected. The collected organic phases wasconcentrated by an evaporator to obtain 20.3 g (yield: 99%) of compound(16-1).CF₃CF₂CF₂—O—(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OSO₂CF₃  (16-1)

NMR spectrum of compound (16-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 4.6 (2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.7 (42F), −74.1 (3F), −76.1 (1F), −79.5 (1F), −82.2 (3F), −89.4 to−91.1 (90F), −130.5 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (16-1): 4,340.

Ex. 1-7

In an 50 mL eggplant flask, 0.13 g of sodium hydride (55%/paraffin) wassuspended in 5.0 g of 1,3-bis(trifluoromethyl)benzene (manufactured byTokyo Chemical Industry Co., Ltd.), and 10.0 g of the compound (16-1)was dropwise added at room temperature. To this, 0.91 g ofHOCH₂C(CH₂OCH₂CH═CH₂)₃ (manufactured by DAISO CO., LTD. purified productof NEOALLYL (registered trademark) P-30M) was added, followed by heatingto 70° C. and stirring for 12 hours. After completion of the reaction,15 g of AK-225 was added, followed by washing with water, whereupon theorganic phase was collected and concentrated by an evaporator. This waspurified by silica gel Column chromatography (developing solvent:AE-3000/ethyl acetate=99/1 (mass ratio)) to obtain 2.6 g (yield: 26%) ofcompound of (17-1).CF₃CF₂CF₂—O—(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂—C(CH₂OCH₂CH═CH₂)₃  (17-1)

NMR spectrum of compound (17-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.6 (6H),3.7 to 3.9 (10H), 5.1 (6H), 5.8 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.7 (42F), −77.2 (1F), −79.4 (1F), −82.2 (3F), −89.4 to −91.1 (90F),−130.5 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (17-1): 4,450.

Ex. 1-8

Into a 10 mL container made of PFA, 2.0 g of the compound (17-1), 0.002g of a xylene solution (platinum content: 2%) of aplatinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, 0.24 g ofHSi(OCH₃)₃, 0.003 g of dimethyl sulfoxide and 0.15 g of1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical IndustryCo., Ltd.) were put and stirred at 40° C. for 4 hours. After completionof the reaction, the solvent, etc. were distilled off under reducedpressure, followed by filtration through a membrane filter having a poresize of 0.2 μm, to obtain 1.9 g (yield 92%) of a composition (1)comprising compound (1A-1) wherein three allyl groups of the compound(17-1) were hydrosilylated and a by-product wherein some or all of threeallyl groups of the compound (17-1) were isomerized to an inner olefin(—CH═CHCH₃). The conversion in the hydrosilylation was 100%, and nocompound (17-1) remained. The selectivity in the hydrosilylation was85%.CF₃CF₂CF₂—O—(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂—C[CH₂OCH₂CH₂CH₂—Si(OCH₃)₃]₃  (1A-1)

NMR spectrum of compound (1A-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.7 (6H),1.7 (6H), 3.4-3.8 (44H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.7 (42F), −77.2 (1F), −79.4 (1F), −82.2 (3F), −89.4 to −91.1 (90F),−130.5 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (1A-1): 4,810.

Ex. 2: Production of Compound (1B-1) Ex. 2-1

30.6 g (yield: 99%) of compound (16B-1) was obtained in the same manneras in Ex. 1-6 except that the compound (15-1) was changed to 30.0 g ofthe compound (11-1) obtained in Ex. 1-1, the amount of1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical IndustryCo., Ltd.) was changed to 30.0 g, the amount of CF₃SO₂Cl (manufacturedby Wako Pure Chemical Industries, Ltd.) was changed to 1.44 g, and theamount of triethylamine was changed to 1.45 g.CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OSO₂CF₃  (16B-1)

NMR spectrum of compound (16B-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 4.2 (2H),4.6 (2H), 5.8 to 6.0 (1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −51.2 to−54.6 (42F), −74.1 (3F), −77.6 (1F), −77.6 (2F), −79.0 (1F), −79.5 (1F),−81.2 (3F), −84.3 to −87.2 (2F), −87.9 to −91.0 (82F), −129.4 (2F),144.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (16B-1): 4,280.

Ex. 2-2

2.4 g (yield: 24%) of compound (17B-1) was obtained in the same manneras in Ex. 1-7, except that the compound (16-1) was changed to thecompound (16B-1), the amount of HOCH₂C(CH₂OCH₂CH═CH₂)₃ was changed to0.92 g.CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂—C(CH₂OCH₂CH═CH₂)₃  (17B-1)

NMR spectrum of compound (17B-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.6 (6H),3.7 to 3.9 (10H), 4.2 (2H), 5.1 (6H), 5.7 to 6.0 (4H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −51.2 to−54.6 (42F), −77.2 (1F), −77.7 (1F), −79.3 (1F), −79.7 (1F), −81.2 (3F),−84.3 to −87.2 (2F), −87.9 to −91.0 (82F), −129.4 (2F), −144.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (17B-1): 4,390.

Ex. 2-3

In the same manner as in Ex. 1-8, except that the compound (17-1) waschanged to 1.8 g of the compound (17B-1) obtained in Ex. 2-2 and theamount of HSi(OCH₃)₃ was changed to 0.22 g, 1.7 g (yield 87%) of acomposition (2) comprising compound (1B-1) wherein three allyl groups inthe compound (17B-1) were hydrosilylated and a by-product wherein someor all of three allyl groups in the compound (17B-1) were isomerized toan inner olefin (—CH═CHCH₃), was obtained. The conversion in thehydrosilylation was 100%, and no compound (17B-1) remained. Theselectivity in the hydrosilylation was 87%.CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂—C[CH₂OCH₂CH₂CH₂—Si(OCH₃)₃]₃  (1B-1)

NMR spectrum of compound (1B-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.7 (6H),1.7 (6H), 3.4-3.8 (44H), 4.2 (2H), 5.8 to 6.0 (1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −51.2 to−54.6 (42F), −77.2 (1F), −77.7 (1F), −79.3 (1F), −79.7 (1F), −81.2 (3F),−84.3 to −87.2 (2F), −87.9 to −91.0 (82F), −129.4 (2F), −144.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (1B-1): 4,760.

Ex. 3: Production of Compound (1C-1) Ex. 3-1

Compound (15C-1) was obtained in accordance with the method described inExample 7 in WO2013/121984.CF₃—O—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3)(CF₂CF₂O)—CF₂CF₂CF₂—CH₂OH  (15C-1).

NMR spectrum of compound (15C-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 2.0 (1H),4.0 (2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −56.2(3F), −84.1 (54F), −89.3 (54F), −91.4 (2F), −123.7 (2F), −126.6 (52F),−128.7 (2F).

Mean value of the unit number x3: 13, number average molecular weight ofthe compound (15C-1): 4,700.

Ex. 3-2

30.6 g (yield: 99%) of compound (16C-1) was obtained in the same manneras in Ex. 1-6 except that the compound (15-1) was changed to thecompound (15C-1) obtained in Ex. 3-1, the amount of CF₃SO₂Cl(manufactured by Wako Pure Chemical Industries, Ltd.) was changed to0.86 g, and the amount of triethylamine was changed to 1.02 g.CF₃—O—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3)(CF₂CF₂O)—CF₂CF₂CF₂—CH₂OSO₂CF₃  (16C-1)

NMR spectrum of compound (16C-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 4.7 (2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −56.3(3F), −74.0 (3F), −84.0 (54F), −89.2 (54F), −91.4 (2F), −122.7 (2F),−123.6 (2F), −26.6 (52F).

Mean value of the unit number x3: 13, number average molecular weight ofthe compound (16C-1): 4,830.

Ex. 3-3

3.9 g (yield: 38%) of compound (17C-1) was obtained in the same manneras in Ex. 1-7 except that the amount of sodium hydride (55%/paraffin)was changed to 0.14 g, the compound (16-1) was changed to the compound(16C-1) obtained in Ex. 3-2, the amount of HOCH₂C(CH₂OCH₂CH═CH₂)₃ waschanged to 0.95 g, and after the completion of the reaction, no dilutionwith AK-225 was conducted.CF₃—O—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3)(CF₂CF₂O)—CF₂CF₂CF₂—CH₂OCH₂—C(CH₂OCH₂CH═CH₂)₃  (17C-1)

NMR spectra of compound (17C-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.6 (6H),3.7 to 3.9 (8H), 4.0 (2H), 5.1 (6H), 5.7 to 6.0 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −56.3(3F), −84.0 (54F), −89.2 (54F), −91.4 (2F), −120.5 (2F), −126.6 (52F),−128.6 (2F).

Mean value of the unit number x3: 13, number average molecular weight ofthe compound (17C-1): 4,940.

Ex. 3-4

In the same manner as in Ex. 1-8 except that the compound (17-1) waschanged to 3.0 g of the compound (17C-1) obtained in Ex. 3-3, the amountof the platinum complex solution was changed to 0.004 g, the amount ofHSi(OCH₃)₃ was changed to 0.40 g, the amount of dimethyl sulfoxide waschanged to 0.006 g, the amount of 1,3-bis(trifluoromethyl)benzene(manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 0.30g, 3.0 g (yield: 93%) of a composition (3) comprising compound (1C-1)wherein three allyl groups in the compound (17C-1) are hydrosilylatedand a by-product wherein part or all of three allyl groups in thecompound (17C-1) were isomerized to an inner olefin (—CH═CHCH₃), wasobtained. The conversion in the hydrosilylation was 100%, and nocompound (17C-1) remained. The selectivity in the hydrosilylation was85%.CF₃—O—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3)(CF₂CF₂O)—CF₂CF₂CF₂—CH₂OCH₂—C[CH₂OCH₂CH₂CH₂—Si(OCH₃)₃]₃  (1C-1)

NMR spectrum of compound (1C-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.7 (6H),1.7 (6H), 3.4-3.8 (44H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −56.3(3F), −84.0 (54F), −89.2 (54F), −91.4 (2F), −120.5 (2F), −126.6 (52F),−128.6 (2F).

Mean value of the unit number x3: 13, number average molecular weight ofthe compound (1C-1): 5,300.

Ex. 4: Production of Compound (1D-1) Ex. 4-1

Into a 200 mL eggplant flask, 10 g of HOCH₂C(CH₂CH═CH₂)₃, 20.0 g of1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical IndustryCo., Ltd.) and 25.5 g of (CF₃SO₂)₂O were put, and in a nitrogenatmosphere, 19.3 g of 2,6-lutidine was dropwise added at 0° C. Themixture was heated to room temperature, followed by stirring for onehour. After completion of the reaction, washing with water wasconducted, whereupon the organic phase was collected, and concentratedby an evaporator. This concentrate was purified by silica gel columnchromatography (developing solvent: hexane/ethyl acetate=85/15 (massratio)), to obtain 15.1 g (yield: 85%) of compound (20).CF₃SO₂OCH₂C(CH₂CH═CH₂)₃  (20)

NMR spectrum of compound (20);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 2.1 (6H),4.3 (2H), 5.0 to 5.2 (6H), 5.6 to 5.8 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −74.0(3F).

Ex. 4-2

5.1 g (yield: 51%) of compound (17D-1) was obtained in the same manneras in Ex. 1-7, except that the compound (16-1) was changed to 0.70 g ofthe compound (20) obtained in Ex. 4-1, and HOCH₂C(CH₂OCH₂CH═CH₂)₃ waschanged to 10.0 g of the compound (15-1) obtained in Ex. 1-5.CF₃CF₂CF₂—O—(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂—C(CH₂CH═CH₂)₃  (17D-1)

NMR spectrum of compound (17D-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 2.1 (6H),3.7 (4H), 5.0 to 5.2 (6H), 5.8 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.7 (42F), −77.2 (1F), −79.4 (1F), −82.2 (3F), −89.4 to −91.1 (90F),−130.5 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (17D-1): 4,350.

Ex. 4-3

In the same manner as in Ex. 1-8 except that the compound (17-1) waschanged to the compound (17D-1) obtained in Ex. 4-2 and the amount ofHSi(OCH₃)₃ was changed to 0.25 g, 1.9 g (yield: 90%) of compound (1D-1)wherein three allyl groups in the compound (17D-1) were hydrosilylated.The conversion in the hydrosilylation was 100% and no compound (17D-1)remained. The selectivity in the hydrosilylation was 100%, and noby-product was formed wherein some or all of three allyl groups in thecompound (17D-1) were isomerized to an inner olefin (—CH═CHCH₃).CF₃CF₂CF₂—O—(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂—C[CH₂CH₂CH₂Si(OCH₃)₃]₃  (1D-1)

NMR spectrum of compound (1D-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.7 (6H),1.7 (6H), 3.4-3.8 (37H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.7 (42F), −77.2 (1F), −79.4 (1F), −82.2 (3F), −89.4 to −91.1 (90F),−130.5 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (1D-1): 4,710.

Ex. 5: Production of Compound (1E-1) Ex. 5-1

5.0 g (yield: 50%) of compound (17E-1) was obtained in the same manneras in Ex. 1-7 except that the compound (16-1) was changed to 0.72 g ofthe compound (20) obtained in Ex. 4-1, HOCH₂C(CH₂OCH₂CH═CH₂)₃ waschanged to 10.0 g of the compound (11-1) obtained in Ex. 1-1, and nodilution with AK-225 was conducted after completion of the reaction.CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂—C(CH₂CH═CH₂)₃  (17E-1)

NMR spectrum of compound (17E-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 2.1 (6H),3.7 to 3.9 (4H), 4.2 (2H), 5.0 to 5.2 (6H), 5.7 to 6.0 (4H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −51.2 to−54.6 (42F), −77.2 (1F), −77.7 (1F), −79.3 (1F), −79.7 (1F), −81.2 (3F),−84.3 to −87.2 (2F), −87.9 to −91.0 (82F), −129.4 (2F), −144.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (17E-1): 4,300.

Ex. 5-2

In the same manner as in Ex. 1-8 except that the compound (17-1) waschanged to 1.8 g of the compound (17E-1) obtained in Ex. 5-1 and theamount of HSi(OCH₃)₃ was changed to 0.23 g, 1.7 g (yield: 87%) ofcompound (1E-1) was obtained wherein three allyl groups in the compound(17E-1) are hydrosilylated. The conversion in the hydrosilylation was100%, and no compound (17E-1) remained. The selectivity of thehydrosilylation was 100%, and no by-product was formed wherein some orall of three allyl groups in the compound (17E-1) were isomerized to aninner olefin (—CH═CHCH₃).CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂—C[CH₂CH₂CH₂—Si(OCH₃)₃]₃  (1E-1)

NMR spectrum of compound (1E-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.7 (6H),1.7 (6H), 3.4-3.8 (37H), 4.2 (2H), 5.8 to 6.0 (1H).

¹⁹F-NMR (2821 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −51.2 to−54.6 (42F), −77.2 (1F), −77.7 (1F), −79.3 (1F), −79.7 (1F), −81.2 (3F),−84.3 to −87.2 (2F), −87.9 to −91.0 (82F), −129.4 (2F), −144.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (1E-1): 4,660.

Ex. 6: Production of Compound (1F-1) Ex. 6-1

4.9 g (yield: 48%) of compound (17F-1) was obtained in the same manneras in Ex. 1-7 except that the compound (16-1) was changed to 0.64 g ofthe compound (20) obtained in Ex. 4-1, HOCH₂C(CH₂OCH₂CH═CH₂)₃ waschanged to 10.0 g of the compound (15C-1) obtained in Ex. 3-1, and nodilution with AK-225 was conducted after completion of the reaction.CF₃—O—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3)(CF₂CF₂O)—CF₂CF₂CF₂—CH₂OCH₂—C(CH₂CH═CH₂)₃  (17F-1)

NMR spectrum of compound (17F-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 2.1 (6H),3.7 to 3.9 (4H), 5.0 to 5.2 (6H), 5.7 to 6.0 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −56.3(3F), −84.0 (54F), −89.2 (54F), −91.4 (2F), −120.5 (2F), −126.6 (52F),−28.6 (2F).

Mean value of the unit number x3: 13, number average molecular weight ofthe compound (17F-1): 4,850.

Ex. 6-2

In the same manner as in Ex. 1-8 except that the compound (17-1) waschanged to the compound (17F-1) obtained in Ex. 6-1, and the amount ofHSi(OCH₃)₃ was changed to 0.23 g, 1.9 g (yield: 90%) of compound (1F-1)was obtained wherein three allyl groups in the compound (17F-1) werehydrosilylated. The conversion in the hydrosilylation was 100%, and nocompound (17F-1) remained. The selectivity in the hydrosilylation was100%, and no by-product was formed wherein some or all of three allylgroups in the compound (17F-1) were isomerized to an inner olefin(—CH═CHCH₃).CF₃—O—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3)(CF₂CF₂O)—CF₂CF₂CF₂—CH₂OCH₂—C[CH₂CH₂CH₂—Si(OCH₃)₃]₃  (1F-1)

NMR spectrum of compound (1F-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.7 (6H),1.7 (6H), 3.4-3.8 (37H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −56.3(3F), −84.0 (54F), −89.2 (54F), −91.4 (2F), −120.5 (2F), −126.6 (52F),−128.6 (2F).

Mean value of the unit number x3: 13, number average molecular weight ofthe compound (1F-1): 5,210.

Ex. 7: Production of Compound (2A-1) Ex. 7-1

31.0 g (yield: 97%) of compound (18-1) was obtained in the same manneras in Ex. 1-6 except that the compound (15-1) was changed to 30.0 g ofthe compound (10-1), the amount of 1,3-bis(trifluoromethyl)benzene(manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 30.0g, the amount of CF₃SO₂Cl (manufactured by Wako Pure ChemicalIndustries, Ltd.) was changed to 2.9 g, and the amount of triethylaminewas changed to 3.0 g.CF₃SO₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OSO₂CF₃  (18-1)

NMR spectrum of compound (18-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 4.6 (2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −51.2 to−54.6 (42F), −74.1 (6F), −77.0 (2F), −79.0 (2F), −87.5 to −91.0 (80F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (18-1): 4,150.

Ex. 7-2

1.5 g (yield: 14%) of compound (19-1) was obtained in the same manner asin Ex. 1-7 except that the amount of sodium hydride (55%/paraffin) waschanged to 0.25 g, the amount of 1,3-bis(trifluoromethyl)benzene(manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 10.0g, the compound (16-1) was changed to the compound (18-1) obtained inEx. 7-1, the amount of HOCH₂C(CH₂OCH₂CH═CH₂)₃ was changed to 1.6 g, andno dilution with AK-225 was conducted after completion of the reaction.(CH₂═CHCH₂OCH₂)₃C—CH₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂—C(CH₂OCH₂CH═CH₂)₃  (19-1)

NMR spectrum of compound (19-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.6 (12H),3.7 to 3.9 (20H), 5.1 (12H), 5.8 (6H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −51.2 to−54.6 (42F), −74.1 (6F), −77.3 (2F), −79.2 (2F), −87.5 to −91.0 (80F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (19-1): 4,360.

Ex. 7-3

In the same manner as in Ex. 1-8 except that the compound (17-1) waschanged to 1.0 g of the compound (19-1) obtained in Ex. 7-2 and theamount of HSi(OCH₃)₃ was changed to 0.40 g, 1.1 g (yield: 96%) of acomposition (7) comprising compound (2A-1) wherein six allyl groups inthe compound (19-1) were hydrosilylated and a by-product wherein some orall of six allyl groups in the compound (19-1) were isomerized to aninner olefin (—CH═CHCH₃), was obtained. The conversion in thehydrosilylation was 100%, and no compound (19-1) remained. Theselectivity in the hydrosilylation was 84%.[(CH₃O)₃Si—CH₂CH₂CH₂OCH₂]₃C—CH₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂—C[CH₂OCH₂CH₂CH₂—Si(OCH₃)₃]₃  (2A-1)

NMR spectrum of compound (2A-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.7 (12H),1.7 (12H), 3.4-3.8 (86H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −51.2 to−54.6 (42F), −77.7 (2F), −79.7 (2F), −87.5 to −91.0 (80F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (2A-1): 5,010.

Ex. 8: Production of Compound (4-1) Ex. 8-1

21.5 g (yield: 98%) of compound (22-1) was obtained in the same manneras in Ex. 1-6 except that the compound (15-1) was changed to thecompound (21-1) (manufactured by SynQuest Laboratories), the amount ofCF₃SO₂Cl (manufactured by Wako Pure Chemical Industries, Ltd.) waschanged to 4.0 g, and the amount of triethylamine was changed to 4.5 g.CF₃CF₂CF₂—O—(CF(CF₃)CF₂O)_(x4)—CF(CF₃)—CH₂OH  (21-1)CF₃CF₂CF₂—O—(CF(CF₃)CF₂O)_(x4)—CF(CF₃)—CH₂OSO₂CF₃  (22-1)

NMR spectrum of compound (22-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 4.9 (2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −74.2(3F), −78.4 to −82.2 (38F), −129.4 (2F), −135.0 (1F), −144.2 (6F).

Mean value of the unit number x4: 6, number average molecular weight ofthe compound (22-1): 1,440.

Ex. 8-2

2.1 g (yield: 20%) of compound (23-1) was obtained in the same manner asin Ex. 1-7 except that the amount of sodium hydride (55%/paraffin) waschanged to 0.05 g, the compound (16-1) was changed to the compound(22-1) obtained in Ex. 8-1, the amount of HOCH₂C(CH₂OCH₂CH═CH₂)₃ waschanged to 0.31 g, and no dilution with AK-225 was conducted after thecompletion of the reaction.CF₃CF₂CF₂—O—(CF(CF₃)CF₂O)_(x4)—CF(CF₃)—CH₂OCH₂—C(CH₂OCH₂CH═CH₂)₃  (23-1)

NMR spectrum of compound (23-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.6 (6H),3.7 to 3.9 (8H), 4.0 (2H), 5.1 (6H), 5.8 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −78.4 to−82.2 (38F), −129.4 (2F), −132.0 (1F), −144.2 (6F).

Mean value of the unit number x4: 6, number average molecular weight ofthe compound (23-1): 1,550.

Ex. 8-3

In the same manner as in Ex. 1-8 except that the compound (17-1) waschanged to the compound (23-1) obtained in Ex. 8-2, the amount of theplatinum complex solution was changed to 0.006 g, the amount ofHSi(OCH₃)₃ was changed to 66 g, and the amount of dimethyl sulfoxide waschanged to 0.01 g, 2.1 g (yield: 85%) of a composition (8) comprisingcompound (4-1) wherein three allyl groups in the compound (23-1) werehydrosilylated, and a by-product wherein some or all of three allylgroups in the compound (23-1) were isomerized to an inner olefin(—CH═CHCH₃), was obtained. The conversion in the hydrosilylation was100%, and no compound (23-1) remained. The selectivity in thehydrosilylation was 85%.CF₃CF₂CF₂—O—(CF(CF₃)CF₂O)_(x4)—CF(CF₃)—CH₂OCH₂—C[CH₂OCH₂CH₂CH₂—Si(OCH₃)₃]₃  (4-1)

NMR spectrum of compound (4-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.7 (6H),1.7 (6H), 3.4-3.8 (41H), 4.0 (2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −78.4 to−82.2 (38F), −129.4 (2F), −132.0 (1F), −144.2 (6F).

Mean value of the unit number x4: 6, number average molecular weight ofthe compound (4-1): 1,920.

Ex. 9: Production of Compound (5-1) Ex. 9-1

Into a 100 mL two-necked eggplant flask, 20.0 g of the compound (15-1)obtained in Ex. 1-5, 0.21 g of tetrabutyl ammonium hydrogen sulfate,1.76 g of BrCH₂CH═CH₂ and 2.6 g of a 30% sodium hydroxide solution wereadded and stirred at 60° C. for 8 hours. After completion of thereaction, 20 g of AC-2000 was added, followed by washing once withdilute aqueous hydrochloric acid, whereupon the organic phase wascollected. The collected organic phase was passed through a silica gelcolumn, whereupon the collected solution was concentrated by anevaporator to obtain 19.8 g (yield: 98.2%) of compound (24-1).CF₃CF₂CF₂—O—(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂CH═CH₂  (24-1).

NMR spectrum of compound (24-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.7 (2H),4.1 (2H), 5.2 to 5.3 (2H), 5.9 (1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.3 to−55.7 (42F), −78.1 (1F), −80.1 (1F), −82.1 (3F), −89.4 to −91.1 (90F),−30.5 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (24-1): 4,250.

Ex. 9-2

In the same manner as in Ex. 1-8 except that the compound (17-1) waschanged to 5.0 g of the compound (24-1) obtained in Ex. 9-1, the amountof the platinum complex solution was changed to 0.005 g, the amount ofHSi(OCH₃)₃ was changed to 0.25 g, the amount of dimethyl sulfoxide waschanged to 0.005 g, the amount of 1,3-bis(trifluoromethyl)benzene(manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 0.20g, and the reaction time was changed to 4 hours, 4.9 g (yield: 95%) of acomposition (9) comprising the compound (5-1) wherein one allyl group inthe compound (24-1) was hydrosilylated and a by-product wherein oneallyl group in the compound (24-1) was isomerized to an inner olefin(—CH═CHCH₃), was obtained. The conversion in the hydrosilylation was100%, and no compound (24-1) remained. The selectivity in thehydrosilylation was 87%.CF₃CF₂CF₂—O—(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂CH₂CH₂—Si(OCH₃)₃  (5-1)

NMR spectrum of compound (5-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.7 (6H),1.7 (6H), 3.6 (11H), 3.8 (2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −52.4 to−55.8 (42F), −78.2 (1F), −80.2 (1F), −82.2 (3F), −89.4 to −91.1 (90F),−130.5 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (5-1): 4,370.

Ex. 10: Production of Compound (5-2) Ex. 10-1

52.4 g (yield: 99.9%) of compound (24-2) was obtained in the same manneras in Ex. 9-1 except that the compound (15-1) was changed to 52.0 g ofthe compound (11-1) obtained in Ex. 1-1, the amount oftetrabutylammonium hydrogen sulfate was changed to 0.52 g, the amount ofBrCH₂CH═CH₂ was changed to 4.4 g, the amount of the 30% sodium hydroxideaqueous solution was changed to 6.5 g, and the amount of AC-2000 waschanged to 50 g.CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂—CH═CH₂  (24-2)

NMR spectrum of compound (24-2);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.7 (2H),4.1 (2H), 4.2 (2H), 5.2 to 5.3 (2H), 5.8 to 6.0 (2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.3 to−55.7 (42F), −78.1 (1F), −78.7 (1F), −80.2 (1F), −80.7 (1F), −82.2 (3F),−85.4 to −88.2 (2F), −89.4 to −91.1 (86F), −130.5 (2F), −145.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (24-2): 4,190.

Ex. 10-2

In the same manner as in Ex. 9-2 except that the compound (24-1) waschanged to the compound (24-2) obtained in Ex. 10-1, 4.8 g (yield: 93%)of a composition (10) comprising compound (5-2) wherein one allyl groupin the compound (24-2) was hydrosilylated and a by-product wherein oneallyl group in the compound (24-2) was isomerized to an inner olefin(—CH═CHCH₃), was obtained. The conversion in the hydrosilylation was100%, and no compound (24-2) remained. The selectivity in thehydrosilylation was 85%.CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂CH₂CH₂—Si(OCH₃)₃  (5-2)

NMR spectrum of compound (5-2);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.7 (6H),1.7 (6H), 3.6 (11H), 3.8 (2H), 4.2 (2H), 5.8 to 6.0 (1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −52.3 to−55.7 (42F), −78.2 (1F), −78.7 (1F), −80.3 (1F), −80.7 (1F), −82.2 (3F),−85.4 to −88.2 (2F), −89.4 to −91.1 (82F), −130.5 (2F), −45.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (5-2): 4,310.

Ex. 11: Production of Compound (1I-1) Ex. 11-1

In accordance with the method described in Example 6 of WO2013/121984,compound (14I-1) was obtained.CF₃—O—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3)(CF₂CF₂O)—CF₂CF₂CF₂—C(O)OCH₃  (14I-1)

NMR spectrum of compound (14I-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.9 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −55.2(3F), −82.1 (54F), −88.1 (54F), −90.2 (2F), −118.2 (2F), −125.4 (52F),−126.2 (2F).

Mean value of the unit number x3: 13, number average molecular weight ofthe compound (14I-1): 4,700.

Ex. 11-2

Into a 50 mL eggplant flask, 9.0 g of the compound (14I-1) obtained inEx. 11-1 and 0.45 g of H₂N—CH₂—C(CH₂CH═CH₂)₃ were put and stirred for 12hours. From NMR, it was confirmed that the compound (14I-1) was allconverted to compounds (17I-1). Further, methanol was formed as aby-product. The obtained solution was diluted with 9.0 g of AE-3000, andpurified by silica gel column chromatography (developing solvent:AE-3000) to obtain 7.6 g (yield: 84%) of compound (17I-1).CF₃—O—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)₃(CF₂CF₂O)—CF₂CF₂CF₂—C(O)NH—CH₂—C(CH₂CH═CH₂)₃  (17I-1)

NMR spectrum of compound (17I-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 2.1 (6H),3.4 (2H), 5.2 (6H), 6.2 to 5.9 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −55.2(3F), −82.1 (54F), −88.1 (54F), −90.2 (2F), −119.6 (2F), −125.4 (52F),−126.2 (2F).

Mean value of the unit number x3: 13, number average molecular weight ofthe compound (17I-1): 4,800.

Ex. 11-3

Into a 10 mL sample tube made of PFA, 6.0 g of the compound (17I-1)obtained in Ex. 11-2, 0.07 g of a xylene solution (platinum content: 2%)of platinum/1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex, 0.78 gof HSi(OCH₃)₃, 0.02 g of dimethyl sulfoxide, and 0.49 g of1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical IndustryCo., Ltd.) were put and stirred at 40° C. for 10 hours. After completionof the reaction, the solvent, etc. were distilled off under reducedpressure, followed by filtration through a membrane filter of 1.0 μmpore size, to obtain 6.7 g (yield: 100%) of compound (1I-1).CF₃—O—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3)(CF₂CF₂O)—CF₂CF₂CF₂—C(O)NH—CH₂—C[CH₂CH₂CH₂—Si(OCH₃)₃]₃  (1I-1)

NMR spectrum of compound (1I-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.75 (6H),1.3 to 1.6 (12H), 3.4 (2H), 3.7 (27H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −55.2(3F), −82.1 (54F), −88.1 (54F), −90.2 (2F), −119.6 (2F), −25.4 (52F),−26.2 (2F).

Mean value of the unit number x3: 13, number average molecular weight ofthe compound (11I-1): 5,400.

Ex. 12: Production of Compound (1I-2) Ex. 12-1

7.5 g (yield: 84%) of compound (17I-2) was obtained in the same manneras in Ex. 11-2 except that instead of 0.45 g of H₂N—CH₂—C(CH₂CH═CH₂)₃,0.41 g of H₂N—C(CH₂CH═CH₂)₃ was used.CF₃—O—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3)(CF₂CF₂O)—CF₂CF₂CF₂—C(O)NH—C(CH₂CH═CH₂)₃  (17I-2)

NMR spectrum of compound (17I-2);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 2.3 (6H),5.2 (6H), 5.9 to 6.2 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −55.2(3F), −82.1 (54F), −88.1 (54F), −90.2 (2F), −119.4 (2F), −125.4 (52F),−126.2 (2F).

Mean value of the unit number x3: 13, number average molecular weight ofthe compound (17I-2): 4,800.

Ex. 12-2

6.7 g (yield: 100%) of compound of (1I-2) was obtained in the samemanner as in Ex. 11-3 except that instead of the compound (17I-1), thecompound (17I-2) obtained in Ex. 12-1 was used.CF₃—O—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3)(CF₂CF₂O)—CF₂CF₂CF₂—C(O)NH—C[CH₂CH₂CH₂—Si(OCH₃)₃]₃  (1I-2)

NMR spectrum of compound (1I-2);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.75 (6H),1.3 to 1.6 (12H), 3.7 (27H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −55.2(3F), −82.1 (54F), −88.1 (54F), −90.2 (2F), −119.4 (2F), −125.4 (52F),−126.2 (2F).

Mean value of the unit number x3: 13, number average molecular weight ofthe compound (1I-2): 5,400.

Ex. 13: Production of Compound (IH-1) Ex. 13-1

In accordance with the method described in J. Org. Chem., Vol. 64, 1999,p. 2564-2566, the compound (11-1) obtained in Ex. 1-1 was oxidized toobtain compound (13H-1).CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—C(O)OH  (13H-1)

NMR spectrum of compound (13H-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 4.2 (2H),5.8 to 6.0 (1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.8 (42F), −78.8 (2F), −80.5 (1F), −80.8 (1F), −82.2 (3F), −85.3 to−88.2 (2F), −89.4 to −91.1 (82F), −130.5 (2F), −145.1 (1F)

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (13H-1): 4,150.

Ex. 13-2

Into a 50 mL eggplant flask, 6.2 g of the compound (13H-1) obtained inEx. 13-1 and 20 mL of methanol were put and stirred at room temperaturefor 12 hours. From NMR, it was confirmed that the compound (13H-1) wasall converted to compound (14H-1). By distilling off the solvent underreduced pressure, 6.2 g (yield: 100%) of the compound (14H-1) wasobtained.CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—C(O)OCH₃  (14H-1)

NMR spectrum of compound (14H-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.9 (3H),4.2 (2H), 5.8 to 6.0 (1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.8 (42F), −77.8 (1F), −78.8 (1F), −79.5 (1F), −80.8 (1F), −82.2 (3F),−85.3 to −88.2 (2F), −89.4 to −91.1 (82F), −130.5 (2F), −145.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (14H-1): 4,150.

Ex. 13-3

4.8 g (yield: 76%) of the compound (17H-1) was obtained in the samemanner as in Ex. 11-2 except that the compound (14I-1) was changed to5.7 g of the compound (14H-1) obtained in Ex. 13-2, and the amount ofH₂N—CH₂—C(CH₂CH═CH₂)₃ was changed to 0.26 g.CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—C(O)NH—CH₂—C(CH₂CH═CH₂)₃  (17H-1)

NMR spectrum of compound (17H-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 2.2 (6H),3.3 (2H), 3.5 (1H), 4.2 (2H), 5.2 (6H), 5.8 to 6.0 (4H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.8 (42F), −78.8 (2F), −79.6 (1F), −80.8 (1F), −82.2 (3F), −85.3 to−88.2 (2F), −89.4 to −91.1 (82F), −130.5 (2F), −145.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (17H-1): 4,250.

Ex. 13-4

3.8 g (yield: 100%) of compound (1H-1) was obtained in the same manneras in Ex. 11-3 except that the compound (17I-1) was changed to 3.5 g ofthe compound (17H-1) obtained in Ex. 13-3, the amount of the platinumcomplex solution was changed to 0.03 g, the amount of HSi(OCH₃)₃ waschanged to 0.5 g, the amount of dimethyl sulfoxide was changed to 0.01g, and the amount of 1,3-bis(trifluoromethyl)benzene (manufactured byTokyo Chemical Industry Co., Ltd.) was changed to 0.35 g.CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—C(O)NH—CH₂—C[CH₂CH₂CH₂—Si(OCH₃)₃]₃  (1H-1)

NMR spectrum of compound (1H-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.75 (6H),1.3 to 1.6 (12H), 3.4 (2H), 3.7 (27H), 5.8 to 6.0 (1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.8 (42F), −78.8 (2F), −79.6 (1F), −80.8 (1F), −82.2 (3F), −85.3 to−88.2 (2F), −89.4 to −91.1 (82F), −130.5 (2F), −145.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (1H-1): 4,600.

Ex. 14: Production of Compound (1H-2) Ex. 14-1

4.7 g (yield: 80%) of compound (17H-2) was obtained in the same manneras in Ex. 13-3 except that instead of 0.26 g of H₂N—CH₂—C(CH₂CH═CH₂)₃,0.24 g of H₂N—C (CH₂CH═CH₂)₃ was used.CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—C(O)NH—C(CH₂CH═H₂)₃  (17H-2)

NMR spectrum of compound (17H-2);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 2.4 (6H),3.5 (1H), 5.2 (6H), 5.8 to 6.0 (4H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.8 (42F), −78.8 (2F), −79.6 (1F), −80.8 (1F), −82.2 (3F), −85.3 to−88.2 (2F), −89.4 to −91.1 (82F), −130.5 (2F), −145.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (17H-2): 4,250.

Ex. 14-2

3.8 g (yield: 100%) of compound (1H-2) was obtained in the same manneras Ex. 13-4 except that the compound (17H-1) was changed to the compound(17H-2) obtained in Ex. 14-1.CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—C(O)NH—C[CH₂CH₂CH₂—Si(OCH₃)₃]₃  (1H-2)

NMR spectrum of compound (1H-2);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.75 (6H),1.3 to 1.7 (12H), 3.4 (2H), 3.7 (27H), 5.8 to 6.0 (1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.8 (42F), −78.8 (2F), −79.6 (1F), −80.8 (1F), −82.2 (3F), −85.3 to−88.2 (2F), −89.4 to −91.1 (82F), −130.5 (2F), −145.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (1H-2): 4,600.

Ex. 15: Production of Compound (1K-1) Ex. 15-1

Into a 50 mL eggplant flask, 1.0 g of CF₂═CFOCF₂CF₂CF₂—C(O)OCH₃ and 0.55g of H₂N—CH₂—C(CH₂CH═CH₂)₃ were put and stirred for 12 hours. From NMR,it was confirmed that CF₂═CFOCF₂CF₂CF₂—C(O)OCH₃ was all converted tocompound (30-1). Further, methanol was formed as a by-product. Theobtained solution was diluted with 6.0 g of AE-3000, followed bypurification by silica gel column chromatography (developing solvent:AE-3000) to obtain 1.3 g (yield: 84%) of the compound (30-1).CF₂═CFOCF₂CF₂CF₂—C(O)NH—CH₂—C(CH₂CH═CH₂)₃  (30-1)

NMR spectrum of compound (30-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 2.1 (6H),3.4 (2H), 5.2 (6H), 5.9 to 6.2 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −84.2(2F), −113.4 to 114.2 (1F), −119.5 (2F), −121.1 to −121.9 (1F), −125.3(2F), −134.5 to −135.3 (1F).

Ex. 15-2

Into a 50 mL eggplant flask, 1.0 g of the compound (30-1) obtained inEx. 15-1, 10 g of the compound (11-1) obtained in Ex. 1-1, 2 g of a 48mass % potassium hydroxide aqueous solution, and 0.1 g of (CH₃)₃COH,were added and stirred at 60° C. for 5 hours. From NMR, it was confirmedthat the compound (1I-1) was all converted to compound (17K-1). To theobtained solution, 20 g of 1N hydrochloric acid was added, and afterconfirming that the aqueous layer became acidic, the organic layer wasseparated and the solvent was distilled off, to obtain 11 g (yield:100%) of the compound (17K-1).CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂CH₂OCF₂CHFOCF₂CF₂CF₂—C(O)NH—CH₂—C(CH₂CH═CH₂)₃  (17K-1)

NMR spectrum of compound (17K-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 2.2 (6H),3.3 (2H), 3.5 (1H), 4.2 (4H), 5.2 (6H), 5.8 to 6.0 (5H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.8 (42F), −78.8 (2F), −79.6 (1F), −80.8 (1F), −82.2 (3F), −84.2 (2F),−85.3 to −88.2 (2F), −89.4 to −91.1 (82F), −119.5 (2F), −125.3 (2F),−130.5 (4F), −145.1 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (17K-1): 4,520.

Ex. 15-3

5.4 g (yield: 100%) of compound (1K-1) was obtained in the same manneras in Ex. 11-3 except that the compound (17I-1) was changed to 5 g ofthe compound (17K-1) obtained in Ex. 15-2, the amount of the platinumcomplex solution was changed to 0.5 mg, the amount of HSi(OCH₃)₃ waschanged to 0.5 g, the amount of dimethyl sulfoxide was changed to 0.01g, and the amount of 1,3-bis(trifluoromethyl)benzene (manufactured byTokyo Chemical Industry Co., Ltd.) was changed to 0.2 g.CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂CH₂OCF₂CHFOCF₂CF₂CF₂—C(O)NH—CH₂—C[CH₂CH₂CH₂—Si(OCH₃)₃]₃  (1K-1)

NMR spectrum of compound (1K-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.75 (6H),1.3 to 1.6 (12H), 3.3 (2H), 3.5 (27H), 4.2 (4H), 5.8 to 6.0 (2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.8 (42F), −78.8 (2F), −79.6 (1F), −80.8 (1F), −82.2 (3F), −84.2 (2F),−85.3 to −88.2 (2F), −89.4 to −91.1 (82F), −119.5 (2F), −125.3 (2F),−130.5 (4F), −145.1 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (1K-1): 4,950.

Ex. 16: Production of Compound (1G-1) Ex. 16-1

In accordance with the method described in Example 4 in WO2014/163004,compound (14-1) was obtained.CF₃CF₂CF₂—O—(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—C(O)OCH₃  (14-1)

NMR spectrum of compound (14-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 3.9 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.8 (42F), −82.2 (3F), −89.4 to −91.1 (92F), −130.5 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (14-1): 4,230.

Ex. 16-2

4.4 g (yield: 85%) of compound (17G-1) was obtained in the same manneras in Ex. 11-2 except that the compound (14I-1) was changed to 5.0 g ofthe compound (14-1) obtained in Ex. 16-1, and the amount ofH₂N—CH₂—C(CH₂CH═CH₂)₃ was changed to 0.2 g.CF₃CF₂CF₂—O—(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—C(O)NH—CH₂—C(CH₂CH═CH₂)₃  (17G-1)

NMR spectrum of compound (17G-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 2.2 (6H),3.3 (2H), 3.5 (1H), 5.2 (6H), 5.8 to 6.0 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.8 (42F), −82.2 (3F), −89.4 to −91.1 (92F), −130.8 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (17G-1): 4,360.

Ex. 16-3

4.3 g (yield: 100%) of compound (1G-1) was obtained in the same manneras in Ex. 11-3 except that the compound (17I-1) was changed to 4 g ofthe compound (17G-1) obtained in Ex. 16-2, the amount of the platinumcomplex solution was changed to 0.4 mg, the amount of HSi(OCH₃)₃ waschanged to 0.33 g, the amount of dimethyl sulfoxide was changed to 0.01g, and the amount of 1,3-bis(trifluoromethyl)benzene (manufactured byTokyo Chemical Industry Co., Ltd.) was changed to 0.2 g.CF₃CF₂CF₂—O—(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—C(O)NH—CH₂—C[CH₂CH₂CH₂—Si(OCH₃)₃]₃  (1G-1)

NMR spectrum of compound (1G-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.75 (6H),1.3 to 1.6 (12H), 3.4 (2H), 3.7 (27H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.8 (42F), −82.2 (3F), −89.4 to −91.1 (92F), −130.8 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (1G-1): 4,720.

Ex. 48: Production of Compound (1D-2) Ex. 48-1

Into a 50 mL three-necked flask, 3.0 g of pentaerythritol (manufacturedby Kanto Chemical Co., Inc.), 7.4 g of a 48% NaOH aqueous solution and10.8 g of dimethyl sulfoxide were put and heated to 60° C., then, 11.5 gof 5-bromo-1-pentene (manufactured by Tokyo Chemical Industry Co., Ltd.)was added and stirred for 4 hours. After washing once with diluteaqueous hydrochloric acid, 16 g of cyclopentyl methyl ether(manufactured by Kanto Chemical Co., Inc.) was added, and an organicphase was collected. The collected solution was concentrated by anevaporator to obtain 6.1 g of a crude product. The crude product wasdeveloped by silica gel column chromatography (developing solvent:hexane/ethyl acetate=90/10 (mass ratio)), to fractionate 3.7 g (yield:49%) of HOCH₂C(CH₂OCH₂CH₂CH₂CH═CH₂)₃.

Ex. 48-2

Into a 50 mL eggplant flask, 3.0 g of HOCH₂C(CH₂OCH₂CH₂CH₂CH═CH₂)₃obtained in Ex. 48-1, 9.0 g of AE-3000 and 1.4 g of 2,6-lutidine wereput, and under a nitrogen atmosphere, 3.8 g of (CF₃SO₂)₂O was dropwiseadded at 0° C. The mixture was heated to room temperature and stirredfor 1 hour. After completion of the reaction, washing with water wasconducted, whereupon the organic phase was collected and concentrated byan evaporator. The concentrate was purified by silica gel columnchromatography (developing solvent: AE-3000) to obtain 4.2 g (yield:99%) of compound (20-2).CF₃SO₂OCH₂C(CH₂OCH₂CH₂CH₂CH═CH₂)₃  (20-2)

NMR spectrum of compound (20-2);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 1.6 (6H),2.0 (6H), 3.4 (12H), 4.5 (2H), 5.0 (6H), 5.8 (3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −75.0(3F).

Ex. 48-3

In a 25 mL eggplant flask, 8.9 g of the compound (15-1) obtained in Ex.1-5, 1.0 g of the compound (20-2) obtained in Ex. 48-2, 11 g of1,3-bis(trifluoromethyl)benzene and 1.4 g of cesium carbonate were putand stirred at 80° C. for 8 hours under a nitrogen atmosphere. Aftercompletion of the reaction, washing with water was conducted, whereuponthe organic phase was collected and concentrated by an evaporator. Theconcentrate was purified by silica gel column chromatography (developingsolvent: AE-3000, followed by AE-3000/ethyl acetate=9/1 (mass ratio)) toobtain 8.2 g (yield: 85%) of compound (17D-2).CF₃CF₂CF₂—O—(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂—C(CH₂OCH₂CH₂CH₂CH═CH₂)₃  (17D-2)

NMR spectrum of compound (17D-2);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 1.6 (6H),2.1 (6H), 3.4 (6H), 3.5 (6H), 3.7 (2H), 3.9 (2H), 4.8 to 5.0 (6H), 5.8(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.4 to−55.7 (42F), −77.2 (1F), −79.4 (1F), −82.2 (3F), −89.4 to −91.1 (90F),−130.5 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (17D-2): 4,540.

Ex. 48-4

In the same manner as in Ex. 1-8 except that the compound (17-1) waschanged to the compound (17D-2) obtained in Ex. 48-3, 2.1 g (yield: 97%)of compound (1D-2) was obtained wherein three vinyl groups in thecompound (17D-2) were hydrosilylated. The conversion in thehydrosilylation was 100%, and no compound (17D-2) remained. Theselectivity in the hydrosilylation was 100%, and no by-product wasformed wherein some or all of three vinyl groups in the compound (17D-2)were isomerized to an inner olefin (—CH═CHCH₃).CF₃CF₂CF₂—O—(CF₂CF₂O)(CF₂CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂—C[CH₂OCH₂CH₂CH₂CH₂CH₂Si(OCH₃)₃]₃  (1D-2)

NMR spectrum of compound (1D-2);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.7 (6H),1.4-1.6 (18H), 3.4 (6H), 3.5 (6H), 3.6 (27H), 3.7 (2H), 3.9 (2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: CFCl₃) δ (ppm): −52.3 to−55.6 (42F), −77.2 (1F), −79.4 (1F), −82.2 (3F), −89.4 to −91.0 (90F),−130.5 (2F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (1D-2): 4,900.

Ex. 49: Production of Compound (1E-2) Ex. 49-1

7.9 g (yield: 83%) of compound (17E-2) was obtained in the same manneras in Ex. 48-3 except that the compound (15-1) was changed to 8.8 g ofthe compound (11-1) obtained in Ex. 1-1.CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂—C(CH₂OCH₂CH₂CH₂CH═CH₂)₃  (17E-2)

NMR spectrum of compound (17E-1);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 1.6 (6H),2.1 (6H), 3.4 (6H), 3.5 (6H), 3.7 (2H), 3.9 (2H), 4.2 (2H), 4.8 to 5.0(6H), 5.8 to 6.0 (4H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −51.2 to−54.6 (42F), −77.2 (1F), −77.7 (1F), −79.3 (1F), −79.7 (1F), −81.2 (3F),−84.3 to −87.2 (2F), −87.9 to −91.0 (82F), −129.4 (2F), −144.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (17E-1): 4,490.

Ex. 49-2

In the same manner as in Ex. 1-8 except that the compound (17D-2) waschanged to the compound (17E-2) obtained in Ex. 49-1, 2.0 g (yield: 92%)of compound (1E-2) was obtained wherein three vinyl groups in thecompound (17E-2) were hydrosilylated. The conversion in thehydrosilylation was 100%, and no compound (17E-2) remained. Theselectivity in the hydrosilylation was 100%, and no by-product wasformed wherein some or all of three vinyl groups in the compound (17E-2)were isomerized to an inner olefin (—CH═CHCH₃).CF₃CF₂CF₂—O—CHFCF₂OCH₂—(CF₂O){(CF₂O)_(x1)(CF₂CF₂O)_(x2)}—CF₂—CH₂OCH₂—C[CH₂OCH₂CH₂CH₂CH₂CH₂—Si(OCH₃)₃]₃  (1E-2)

NMR spectrum of compound (1E-2);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.7 (6H),1.4-1.6 (18H), 3.4 (6H), 3.5 (6H), 3.6 (27H), 3.7 (2H), 3.9 (2H), 4.2(2H), 5.8 to 6.0 (1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −51.2 to−54.6 (42F), −77.2 (1F), −77.7 (1F), −79.3 (1F), −79.7 (1F), −81.2 (3F),−84.3 to −87.2 (2F), −87.9 to −91.0 (82F), −129.4 (2F), −144.1 (1F).

Mean value of the unit number x1: 21, mean value of the unit number x2:20, number average molecular weight of the compound (1E-2): 4,850.

Ex. 50: Production of Compound (1F-2) Ex. 50-1

8.8 g (yield: 83%) of compound (17F-2) was obtained in the same manneras in Ex. 48-3 except that the compound (15-1) was changed to 9.9 g ofthe compound (15C-1) obtained in Ex. 3-1.CF₃—O—(C F₂CF₂O—CF₂CF₂C F₂CF₂O)_(x3)(CF₂CF₂O)—CF₂CF₂CF₂—CH₂OCH₂—C(CH₂OCH₂CH₂CH₂CH═CH₂)₃  (17F-2)

NMR spectrum of compound (17F-2);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 1.6 (6H),2.1 (6H), 3.4 (6H), 3.5 (6H), 3.7 (2H), 3.9 (2H), 4.8 to 5.0 (6H), 5.8(3H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −56.3(3F), −84.0 (54F), −89.2 (54F), −91.4 (2F), −120.5 (2F), −126.6 (52F),−128.6 (2F).

Mean value of the unit number x3: 13, number average molecular weight ofthe compound (17F-2): 5,040.

Ex. 50-2

In the same manner as in Ex. 1-8 except that the compound (17D-2) waschanged to the compound (17F-2) obtained in Ex. 50-1, 2.1 g (yield: 98%)of compound (1F-2) was obtained wherein three vinyl groups in thecompound (17F-2) were hydrosilylated. The conversion in thehydrosilylation was 100%, and no compound (17F-2) remained.

The selectivity in the hydrosilylation was 100%, and no by-product wasformed wherein some or all of three vinyl groups in the compound (17F-2)were isomerized to an inner olefin (—CH═CHCH₃).CF₃—O—(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x3)(CF₂CF₂O)—CF₂CF₂CF₂—CH₂OCH₂—C[CH₂OCH₂CH₂CH₂CH₂CH₂—Si(OCH₃)₃]₃  (1F-2)

NMR spectrum of compound (1F-2);

¹H-NMR (300.4 MHz, solvent: CDCl₃, reference: TMS) δ (ppm): 0.7 (6H),1.4-1.6 (18H), 3.4 (6H), 3.5 (6H), 3.6 (27H), 3.7 (2H), 3.9 (2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, reference: C₆F₆) δ (ppm): −56.3(3F), −84.0 (54F), −89.2 (54F), −91.4 (2F), −120.5 (2F), −126.6 (52F),−128.6 (2F).

Mean value of the unit number x3: 13, number average molecular weight ofthe compound (1F-1): 5,400.

Ex. 17 to 32 and 51 to 53: Production and Evaluation of Articles

Surface treatment of a substrate was conducted by using the compound orcomposition obtained in each of Ex. 1 to 16 and 48 to 50, to obtain anarticle in each of Ex. 17 to 32 and 51 to 53. As the surface treatmentmethod, each of the following dry coating method and wet coating method,was used in each Ex. As the substrate, chemically strengthened glass wasused. With respect to the obtained article, evaluations were conductedby the following methods. The results are shown in Tables 1 to 4.

(Dry Coating Method)

Dry coating was conducted by means of a vacuum vapor depositionapparatus (manufactured by ULVAC Co., VTR-350M) (vacuum vapor depositionmethod). 0.5 g of the compound or composition obtained in each of Ex. 1to 16 and 48 to 50 was filled into a molybdenum boat in the vacuum vapordeposition apparatus, and inside of the vacuum vapor depositionapparatus was evacuated to a level of at most 1×10⁻³ Pa. The boat havingthe composition placed therein was heated at a temperature raising rateof at most 10° C./min, and at the time when the vapor deposition rate bya quartz oscillator film thickness meter exceeded 1 nm/sec., the shutterwas opened to initiate film deposition on the surface of the substrate.At the time when the film thickness became about 50 nm, the shutter wasclosed to terminate film deposition on the surface of the substrate. Thesubstrate to which the composition was deposited, was heat-treated at200° C. for 30 minutes, followed by washing with AK-225, to obtain anarticle having a surface-treated layer on the surface of the substrate.

(Wet Coating Method)

The compound or composition obtained in each of Ex. 1 to 16 and 48 to50, and C₄F₉OC₂H₅ (manufactured by 3M, Novec (registered trademark)7200) as a liquid medium, were mixed to prepare a coating liquid havinga solid content concentration of 0.05%. A substrate was dipped in thecoating liquid and allowed to stand for 30 minutes, whereupon thesubstrate was withdrawn (dip coating method). The coating film was driedat 200° C. for 30 minutes and washed with AK-225, to obtain an articlehaving a surface-treated layer on the surface of the substrate.

(Evaluation Methods)

<Method for Measuring Contact Angle>

A contact angle of about 2 μL of distilled water or n-hexadecane placedon the surface of the surface layer, was measured by using a contactangle measuring apparatus (manufactured by Kyowa Interface Science Co.,Ltd. DM-500). Measurements were conducted at five different points onthe surface of the surface layer, and the average value was calculated.For the calculation of the contact angle, a 2θ method was employed.

<Initial Contact Angle>

With respect to the surface layer, the initial water contact angle andthe initial n-hexadecane contact angle were measured by theabove-mentioned measuring method.

The evaluation standards are as follows.

Initial water contact angle:

⊚ (excellent): at least 115 degrees.

◯ (good): at least 110 degrees and less than 115 degrees.

Δ (acceptable): at least 100 degrees and less than 110 degrees.

x (poor): less than 100 degrees.

Initial n-hexadecane contact angle:

⊚ (excellent): at least 66 degrees.

◯ (good): at least 65 degrees and less than 66 degrees.

Δ (acceptable): at least 63 degrees and less than 65 degrees.

x (poor): less than 63 degrees.

<Abrasion Resistance>

With respect to the surface layer, in accordance with JIS L0849: 2013(ISO 105-X12: 2001), using a reciprocating traverse testing machine(manufactured by KNT Co.), steel wool Bon Star (#0000) was reciprocated10,000 times under a pressure of 98.07 kPa at a speed of 320 cm/min, tomeasure the water contact angle. The smaller the decrease in waterrepellency (water contact angle) after the abrasion, the smaller thedecrease in performance due to the abrasion, and the better the abrasionresistance.

The evaluation standards are as follows.

⊚ (excellent): The change in water contact angle after reciprocation of10,000 times is at most 5 degrees.

◯ (good): The change in water contact angle after reciprocation of10,000 times is more than 5 degrees and at most 10 degrees.

Δ (acceptable): The change in water contact angle after reciprocation of10,000 times is more than 10 degrees and at most 20 degrees.

x (poor): The change in water contact angle after reciprocation of10,000 is more than 20 degrees.

<Outer Appearance>

The haze of an article was measured by a haze meter (manufactured byToyo Seiki Seisaku-sho, Ltd.). The smaller the haze, the more uniformthe coating of the fluorinated ether compound, and the better the outerappearance. The evaluation standards are as follows.

⊚ (excellent): The haze is at most 0.1%.

◯ (good): The haze is more than 0.1% and at most 0.2%.

Δ (acceptable): The haze is more than 0.2% and at most 0.3%.

x (poor): The haze is more than 0.3%.

<Fingerprint Stain Removability>

An artificial fingerprint liquid (liquid consisting of oleic acid andsqualene) was deposited on the flat surface of a silicon rubber plug,and extra oil was wiped off by a nonwoven fabric (manufactured by AsahiKasei Corporation, BEMCOT (registered trademark) M-3), to prepare astamp for fingerprint. Such a fingerprint stamp was placed on thesurface layer and pressed with a load of 9.8N for 10 seconds. The hazeat a portion where the fingerprint adhered, was measured by a hazemeter, and taken as an initial value. With respect to the portion wherethe fingerprint adhered, using a reciprocating traverse testing machine(manufactured by KNT Co.) having a tissue paper attached, wiping wasconducted with a load of 4.9N. The value of haze was measured every onereciprocation wiping, and the number of wiping times where the hazebecame at most 10% from the initial value, was measured. The smaller thenumber of wiping times, the easier the removal of the fingerprint, andthe better the fingerprint stain removability. The evaluation standardsare as follows.

⊚ (excellent): The number of wiping times is at most 3 times.

◯ (good): The number of wiping times is from 4 to 5 times.

Δ (acceptable): The number of wiping times is from 6 to 8 times.

x (poor): The number of wiping times is at least 9 times.

<Light Resistance>

To the surface layer, using a tabletop xenon arc lamp type acceleratedlight resistance testing machine (manufactured by Toyo SeikiSeisaku-sho, Ltd., SUNTEST XLS+), at a black panel temperature of 63°C., light (650 W/m², 300 to 700 nm) was irradiated for 500 hours,whereupon the water contact angle was measured. The smaller the decreasein the water contact angle after the accelerated light resistance test,the smaller the decrease in the performance due to light, and the betterthe light resistance. The evaluation standards are as follows.

⊚ (excellent): The change in water contact angle after the acceleratedlight resistance test is at most 5 degrees.

◯ (good): The change in water contact angle after the accelerated lightresistance test is more than 5 degrees and at most 10 degrees.

Δ (acceptable): The change in water contact angle after the acceleratedlight resistance test is more than 10 degrees and at most 20 degrees.

x (poor): The change in water contact angle after the accelerated lightresistance test is more than 20 degrees.

<Lubricity>

The dynamic friction coefficient of the surface layer to an artificialskin (manufactured by Idemitsu Technofine Co., PBZ13001) was measured byusing a load variation type friction wear test system (manufactured byShinto Scientific Co., Ltd. HHS2000) under conditions of a contact area:3 cm×3 cm, and a load: 0.98N. The smaller the dynamic frictioncoefficient, the better the lubricity. The evaluation standards are asfollows.

⊚ (excellent): The dynamic friction coefficient is at most 0.3.

◯ (good): The dynamic friction coefficient is more than 0.3 and at most0.4.

Δ (acceptable): The dynamic friction coefficient is more than 0.4 and atmost 0.5.

x (poor): The dynamic friction coefficient is more than 0.5.

TABLE 1 Ex. 17 18 19 20 21 Fluorinated ether Type Composition (1):Composition (2): Composition (3): Compound Compound compound/ compound(1A-1) + compound (1B-1) + compound (1C-1) + (1D-1) (1E-1) compositionBy-product By-product By-product Conversion (%) in hydrosilylation 100100 100 100 100 Selectivity (%) in hydrosilylation 85 87 85 100 100 Drycoating method Initial contact Water ⊚ ◯ ⊚ ⊚ ◯ angle n-Hexadecane ⊚ ⊚ ⊚⊚ ⊚ Abrasion resistance ◯ ◯ ◯ ⊚ ⊚ Wet coating method Initial contactWater ⊚ ◯ ⊚ ⊚ ◯ angle n-Hexadecane ⊚ ⊚ ⊚ ⊚ ⊚ Abrasion resistance ◯ ◯ ◯ ◯◯ Outer appearance ◯ ⊚ ◯ ◯ ⊚ Fingerprint stain removability ⊚ ⊚ ⊚ ⊚ ⊚Light resistance Δ Δ Δ ◯ ◯ Lubricity ⊚ ⊚ ◯ ⊚ ⊚

TABLE 2 Ex. 22 23 24 25 26 Fluorinated ether Type Compound Composition(7): Composition (8): Composition (9): Composition (10): compound/(1F-1) compound (2A-1) + compound (4-1) + compound (5-1) + compound(5-2) + composition By-product By-product By-product By-productConversion (%) in hydrosilylation 100 100 100 100 100 Selectivity (%) inhydrosilylation 100 84 85 87 85 Dry coating method Initial contact Water⊚ Δ ⊚ ⊚ ◯ angle n-Hexadecane ⊚ Δ ⊚ ⊚ ⊚ Abrasion resistance ◯ X X X X Wetcoating method Initial contact Water ⊚ Δ ⊚ ⊚ ◯ angle n-Hexadecane ⊚ Δ ⊚⊚ ⊚ Abrasion resistance ◯ X X X X Outer appearance ◯ X ◯ ◯ ⊚ Fingerprintstain removability ⊚ X ◯ ⊚ ⊚ Light resistance ⊚ X Δ X X Lubricity ◯ Δ X⊚ ⊚

TABLE 3 Ex. 27 28 29 30 31 32 Fluorinated ether Type Compound CompoundCompound Compound Compound Compound compound (1I-1) (1I-2) (1H-1) (1H-2)(1K-1) (1G-1) Conversion (%) in hydrosilylation 100 100 100 100 100 100Selectivity (%) in hydrosilylation 100 100 100 100 100 100 Dry coatingmethod Initial contact Water ⊚ ⊚ ◯ ◯ ◯ ⊚ angle n-Hexadecane ⊚ ⊚ ⊚ ⊚ ⊚ ⊚Abrasion resistance ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Wet coating method Initial contact Water⊚ ⊚ ◯ ◯ ◯ ⊚ angle n-Hexadecane ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Abrasion resistance ◯ ◯ ◯ ◯ ◯⊚ Outer appearance ◯ ◯ ⊚ ⊚ ⊚ ◯ Fingerprint stain removability ⊚ ⊚ ⊚ ⊚ ⊚⊚ Light resistance ◯ ◯ ◯ ◯ ◯ ⊚ Lubricity ◯ ◯ ⊚ ⊚ ⊚ ⊚

TABLE 4 Ex. 51 52 53 Fluorinated ether Type Compound Compound Compoundcompound/composition (1D-2) (1E-2) (1F-2) Conversion (%) inhydrosilylation 100 100 100 Selectivity (%) in hydrosilylation 100 100100 Dry coating method Initial contact Water ⊚ ◯ ⊚ angle n-Hexadecane ⊚⊚ ⊚ Abrasion resistance ⊚ ⊚ ⊚ Wet coating method Initial contact Water ⊚◯ ⊚ angle n-Hexadecane ⊚ ⊚ ⊚ Abrasion resistance ◯ ◯ ◯ Outer appearance◯ ⊚ ◯

In Ex. 17 to 22, 27 to 32 and 51 to 53 wherein the present compoundhaving three hydrolyzable silyl groups at one terminal, or a compositioncontaining the present compound, was used, the water/oil repellency,abrasion resistance, outer appearance, fingerprint stain removability,light resistance and lubricity were excellent.

In Ex. 23 wherein a composition containing the compound (2A-1) havingthree hydrolyzable silyl groups at both terminals, the abrasionresistance, outer appearance, fingerprint stain removability and lightresistance were inferior. The reason as to why the fingerprint stainremovability was inferior, is considered to be such that unreactedterminal groups reduced the surface physical properties. The reason asto why the outer appearance and abrasion resistance were inferior, isconsidered to be due to reduction in uniformity due to agglomeration ofthe terminal non-fluorine portions. The reason for the inferior abrasionresistance is considered to be such that both terminals were fixed tothe substrate.

In Ex. 24 wherein a composition containing the compound (4-1) wherein apoly(oxyperfluoroalkylene) chain had a branched structure, was used, thelubricity was significantly reduced by a decrease in molecular mobilitydue to the branched structure, and it is considered that abrasionresistance was also thereby greatly reduced.

In Ex. 25 and 26 wherein a composition containing the compound (5-1) orcompound (5-2) having only one hydrolyzable silyl group at one terminal,was used, the abrasion resistance and light resistance were inferior.

Ex. 33 to 47: Production and Evaluation of Articles

Compound (3A-1) isolated in Ex. 1-1, was prepared.

The composition containing compound (1B-1) obtained in Ex. 2-3 waspurified to obtain the compound (1B-1).

The composition containing compound (2A-1) obtained in Ex. 7-3 waspurified to obtain the compound (2A-1).

In the proportions shown in Table 5, the compound (1B-1), the compound(2A-1) and the compound (3A-1) were mixed to prepare compositions. Byusing each composition, an article was prepared by the above-describedwet coating method. With respect to the article, measurement of thecontact angle and evaluation of the abrasion resistance and lubricitywere carried out. The results are shown in Table 5.

TABLE 5 Ex. 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 Compound (3A-1)(%) 0 0 0 0 0 5 10 20 30 40 5 10 15 25 30 Compound (1B-1) (%) 95 90 8070 60 95 90 80 70 60 90 80 70 50 40 Compound (2A-1) (%) 5 10 20 30 40 00 0 0 0 5 10 15 25 30 Initial contact angle Water ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯◯ ◯ ◯ Δ n-Hexadecane ⊚ ⊚ ⊚ ◯ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ◯ ◯ Abrasion resistance ⊚⊚ ◯ Δ X ◯ ◯ ◯ Δ X ⊚ ⊚ ◯ X X Lubricity ⊚ ⊚ ◯ Δ X ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ◯ Δ

From Ex. 33 to 37, it was found that in a case where when the compound(2A-1) having three hydrolyzable silyl groups at both terminals, wasadded to the present compound having three hydrolyzable silyl groups atone terminal, when the proportion of the compound (2A-1) was less than40 mass %, the surface layer had a practical performance. As theproportion of the compound (2A-1) was increased, the abrasion resistanceand lubricity tended to decrease.

From Ex. 38 to 42, it was found that in a case where the compound (3A-1)having no hydrolyzable silyl group at both terminals, was added to thepresent compound having three hydrolyzable silyl groups at one terminal,when the proportion of the compound (3A-1) was less than 40 mass %, thesurface layer had a practical performance. As the proportion of thecompound (3A-1) was increased, the abrasion resistance tended todecrease.

From Ex. 43 to 47, it was found that in a case where the compound (2A-1)having three hydrolyzable silyl groups at both terminals and thecompound (3A-1) having no hydrolyzable silyl group at both terminalswere simultaneously added to the present compound having threehydrolyzable silyl groups at one terminal, when the total proportion ofthe compound (2A-1) and the compound (3A-1) was less than 40 mass %, thesurface layer had a practical performance. As the total proportion ofthe compound (2A-1) and the compound (3A-1) was increased, the abrasionresistance tended to decrease.

INDUSTRIAL APPLICABILITY

The fluorinated ether compound of the present invention can be suitablyused for surface treatment for imparting water/oil repellency to thesurface of a substrate or the like constituting the surface to betouched with a finger, of a touch panel.

What is claimed is:
 1. A fluorinated ether compound represented byformula (1):A¹-O—(R^(f1)O)_(m1)-Q¹-C(O)N(R¹)—R¹¹—C[—R¹²—SiR¹³ _(n1)X¹ _(3-n1)]₃  (1)wherein A¹ is a C₁₋₂₀ perfluoroalkyl group, R^(f1) is a fluoroalkylenegroup having no branched structure, m1 is an integer of from 2 to 210,(R^(f1)O)_(m1) is optionally one composed of at least two types ofR^(f1)O, Q¹ is a single bond or a fluoroalkylene group having nobranched structure, R¹ is a hydrogen atom or an alkyl group, R¹¹ is asingle bond, an alkylene group, an alkylene group having an ethericoxygen atom at a terminal thereof, which is the terminal on the sidebonded to C[—R¹²—SiR¹³ _(n1)X¹ _(3-n1)]₃, an alkylene group with atleast two carbon atoms, having an etheric oxygen atom between two carbonatoms, or an alkylene group with at least two carbon atoms, having anetheric oxygen atom between two carbon atoms and at a terminal thereofwhich is the terminal on the side bonded to C[—R¹²—SiR¹³ _(n1)X¹_(3-n1)]₃, R¹² is an alkylene group, an alkylene group having an ethericoxygen atom at a terminal thereof, which is not the terminal on the sidebonded to Si, or an alkylene group with at least two carbon atoms,having an etheric oxygen atom between two carbon atoms, R¹³ is ahydrogen atom or a monovalent hydrocarbon group, X¹ is a hydrolyzablegroup, n1 is an integer of from 0 to 2, and three [—R¹²—SiR¹³ _(n1)X¹_(3-n1)] are optionally not all the same group.
 2. The fluorinated ethercompound according to claim 1, wherein the fluorinated ether compoundrepresented by the formula (1) is a fluorinated ether compoundrepresented by formula (1-1):A¹-O—(R^(f5)O)_(m5)(R^(F1)O)_(m10)(R^(f6)O)_(m6)-Q¹-C(O)N(R¹)—R¹¹—C[—R¹²—SiR¹³_(n1)X¹ _(3-n1)]₃  (1-1) wherein A¹, Q¹, R¹, R¹¹, R¹², R¹³, X¹ and n1are the same as in the formula (1), R^(F1) is a perfluoroalkylene grouphaving no branched structure, m10 is an integer of at least 2, and(R^(F1)O)_(m10) is optionally one composed of at least two types ofR^(F1)O, R^(f5) is a fluoroalkylene group comprising at least onehydrogen atom and having no branched structure, m5 is an integer of from0 to 4, and when m5 is an integer of from 2 to 4, (R^(f5)O)_(m5) isoptionally one composed of at least two types of R^(f5)O, R^(f6) is afluoroalkylene group comprising at least one hydrogen atom and having nobranched structure, m6 is an integer of from 0 to 4, and when m6 is aninteger of from 2 to 4, (R^(f6)O)_(m6) is optionally one composed of atleast two types of R^(f6)O, andm10+m5+m6=m1.
 3. The fluorinated ether compound according to claim 2,wherein R^(F1) is a C₁₋₆ perfluoroalkylene group, and R^(f5) and R^(f6)are each independently a C₂₋₆ fluoroalkylene group.
 4. The fluorinatedether compound according to claim 2, wherein R^(f5) and R^(f6) are eachindependently a fluoroalkylene group having one or two hydrogen atoms.5. The fluorinated ether compound according to claim 2, wherein m6 is 0and Q¹ is a fluoroalkylene group.
 6. The fluorinated ether compoundaccording to claim 2, wherein m10 is at least
 5. 7. The fluorinatedether compound according to claim 1, wherein when Q¹ is a fluoroalkylenegroup, which is a C₁₋₆ perfluoroalkylene group.
 8. The fluorinated ethercompound according to claim 1, wherein R¹¹ is a single bond or a C₁₋₄alkylene group.
 9. The fluorinated ether compound according to claim 1,wherein R¹² is a C₂₋₆ alkylene group, or a C₃₋₈ alkylene group having anetheric oxygen atom between two carbon atoms.
 10. The fluorinated ethercompound according to claim 1, which has a number average molecularweight of from 500 to 20,000.
 11. A fluorinated ether compositioncomprising the fluorinated ether compound as defined in claim 1, and anadditional fluorinated ether compound other than the fluorinated ethercompound represented by the formula (1), wherein the total proportion ofthe fluorinated ether compound represented by the formula (1) and theadditional fluorinated ether compound in the fluorinated ethercomposition is from 80 to 100 mass %, and the proportion of theadditional fluorinated ether compound to the total of the fluorinatedether compound represented by the formula (1) and the additionalfluorinated ether compound is more than 0 mass % and less than 40 mass%.
 12. The fluorinated ether composition according to claim 11, whereinthe additional fluorinated ether compound is at least one memberselected from the group consisting of a fluorinated ether compound (2),a fluorinated ether compound (3) and a following fluorinated ethercompound (4), wherein the fluorinated ether compound (2) is afluorinated ether compound, in which a group having —C[—R¹²—SiR¹³_(n1)X¹ _(3-n1)]₃ is bonded to both sides of (R^(f1)O)_(m1), thefluorinated ether compound (3) is a fluorinated ether compound, in whicha group having A¹ is bonded to both sides of (R^(f1)O)_(m1), thefluorinated ether compound (4) is a fluorinated ether compound, in whichin the formula (1), —C[—R¹²—SiR¹³ _(n1)X¹ _(3-n1)]₃ is substituted by—C[—R¹²—SiR¹³ _(n1)X¹ _(3-n1)]_(3-t)[—R¹⁵]_(t), wherein R¹⁵ is anunsaturated bond-containing group which becomes —R¹²—SiR¹³ _(n1)X¹_(3-n1) by addition of HSiR¹³ _(n1)X¹ _(3-n1), or an isomer group of theunsaturated bond-containing group, and t is an integer of 1 to
 3. 13. Acoating liquid comprising a fluorinated ether compound as defined inclaim 1, and a liquid medium.
 14. A coating liquid comprising afluorinated ether composition as defined in claim 11, and a liquidmedium.
 15. An article comprising a surface layer which is formed of afluorinated ether compound as defined in claim
 1. 16. An articlecomprising a surface layer which is formed of a fluorinated ethercomposition as defined in claim 11.